CN105189651A - Blends containing photoactive additive - Google Patents

Blends containing photoactive additive Download PDF

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Publication number
CN105189651A
CN105189651A CN201480016229.2A CN201480016229A CN105189651A CN 105189651 A CN105189651 A CN 105189651A CN 201480016229 A CN201480016229 A CN 201480016229A CN 105189651 A CN105189651 A CN 105189651A
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polycarbonate
blend
resin
photo sensitive
group
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CN201480016229.2A
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CN105189651B (en
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让-弗朗索瓦·莫里聚尔
保罗·迪安·西贝特
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SABIC Global Technologies BV
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SABIC Innovative Plastics IP BV
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C08G64/14—Aromatic polycarbonates not containing aliphatic unsaturation containing a chain-terminating or -crosslinking agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Polymeric blends having improved flame retardance properties and good ductility at low temperatures are disclosed. The blend is formed from (A) a photoactive additive that is a cross-linkable polycarbonate resin containing a photoactive group derived from a dihydroxybenzophenone; and (B) a polymer resin which is different from the photoactive additive. The additive can be a compound, oligomer, or polymer. When exposed to ultraviolet light, crosslinking will occur between the photoactive additive and the polymer resin, enhancing the chemical resistance and flame retardance while maintaining ductility.

Description

Blend containing photo sensitive additive
Background technology
This application claims the right of priority of the U.S. Provisional Patent Application series number 61/792,966 of the U.S. Provisional Patent Application series number submission on March 15th, 61/792,912 and 2013 submitted on March 15th, 2013.Being disclosed in this and being all incorporated into this by reference of each application.
Present disclosure relates to polymeric blend (blend polymer), and this polymeric blend contains photo sensitive additive and is different from the non-photosensitivity polymeric base resin of this photo sensitive additive itself.More specifically, this additive comprises the photosensitive group derived from dihydroxy benaophenonel.After being exposed to ultraviolet radiation, photo sensitive additive will be cross-linked with himself and/or be cross-linked with polymeric matrix, improve overall chemical resistant properties, flame retardant resistance and other characteristics.Also disclose the product (such as moulded product, plate, film, molded components etc.) formed by such blend.
Polycarbonate (PC) has the engineering science thermoplastic resin of expected performance as the synthesis of high impact strength and toughness, thermotolerance, weathering resistance and ozon and good ductility.Resin and the blend of carbonate polymer/containing carbonate polymer also show flame retardant properties.But, polymkeric substance drippage so when exposed to flame, and this behavior reduces along with wall thickness and worsens.This behavior reduces their uses in the transparent and opaque thin-walled application requiring V0 or 5VA flame retardant resistance grade widely.These polymkeric substance also have the chemical resistant properties of relative mistake.Expect to provide the additive that can improve these performances.
Summary of the invention
Present disclosure relates to the polymeric blend of the cross-linking properties with improvement.Blend comprises photo sensitive additive, and this photo sensitive additive can be used for cross-linked resin (such as polycarbonate) and improves their flame retardant resistance and chemical resistant properties.In a particular embodiment, photo sensitive additive is the Copolycarbonate containing dihydroxy benaophenonel monomer, and this monomer can be cross-linked when being exposed to ultraviolet (UV) radiation.
Be polymeric blend in various embodiments, comprise: photo sensitive additive, this photo sensitive additive is containing the crosslinkable polycarbonate resin derived from the photosensitive group of dihydroxy benaophenonel; And fluoropolymer resin, this fluoropolymer resin is different from this photo sensitive additive.
Fluoropolymer resin is polyester, polyestercarbonate, bisphenol A homopolycarbonate, Copolycarbonate, tetrabromobisphenol a polycarbonate multipolymer, polysiloxane-altogether-bisphenol-a polycarbonate, polyesteramide, polyimide, polyetherimide, polyamidoimide, polyethers, polyethersulfone, polyepoxide, polylactide, poly(lactic acid) (PLA) or their any combination sometimes.
In other embodiments, fluoropolymer resin is vinyl polymer, rubber-modified graft copolymer, acrylate copolymer, polyacrylonitrile, polystyrene, polyolefine, polyester, polyesteramide, polysiloxane, urethane, polymeric amide, polyamidoimide, polysulfones, polyepoxide, polyethers, polyimide, polyetherimide, polyphenylene oxide, polyphenylene sulfide, polyetherketone, polyethers ether copper, ABS resin, ASA resin, polyethersulfone, Polyphenylene Sulfone, poly-(alkenyl aroma race) polymkeric substance, polyhutadiene, polyacetal, polycarbonate, polyphenylene oxide, vinyl-vinyl acetate copolymer, polyvinyl acetate, liquid crystalline polymers, ethylene-tetrafluoroethylene copolymer, aromatic polyester, fluorinated ethylene propylene, polyvinylidene difluoride (PVDF), polyvinylidene chloride, tetrafluoroethylene, polylactide, poly(lactic acid) (PLA), polycarbonate-organopolysiloxane segmented copolymer, or comprise (i) aromatic ester, (ii) ester carbonic ether (estercarbonate), (iii) multipolymer of carbonate repetitive unit.
Sometimes, fluoropolymer resin is poly-(isophthalic acid ester-terephthalate-resorcinol)-altogether-(bisphenol a carbonate) multipolymer of homo-polycarbonate, Copolycarbonate, polycarbonate-polysiloxane copolymer, polyester-polycarbonate or p-cumylphenol end-blocking.Fluoropolymer resin can be poly-(isophthalic acid ester-terephthalate-resorcinol)-altogether-(bisphenol-a carbonate) polymkeric substance of p-cumylphenol end-blocking or have the polycarbonate-polysiloxane copolymer of 0.4wt% to 25wt% polysiloxane level.Polycarbonate-polysiloxane copolymer can be have the siloxane blocks Copolycarbonate of the siloxane chain length of 10 to 200 containing 6wt% siloxanes (± 10%) of having an appointment to about 20wt% siloxanes (± 10%).
In other embodiments, fluoropolymer resin is polyphosphonates polymkeric substance, polyphosphonates multipolymer or poly-(polyphosphonates)-altogether-(BPA carbonic ether) multipolymer.
Alternatively, fluoropolymer resin can be selected from by the following group formed: polycarbonate-polysiloxane copolymer; There is the aliphatic chain containing at least two carbon atoms polycarbonate resin as repeating unit in the polymer backbone; Ethylene-acrylate-glycidyl acrylate terpolymer; Copolyester polymer; Bisphenol A homopolycarbonate; Poly styrene polymer; Poly-(methyl methacrylate) polymkeric substance; Thermoplastic polyester; Polybutylene terephthalate polymkeric substance; MBS; Acrylonitrile-butadiene-styrene copolymer; Dimethyl bisphenol cyclohexane-altogether-bisphenol-A copolymer; Polyetherimide; Polyethersulfone; Two (4-hydroxyphenyl)-3,3, the 5-trimethyl-cyclohexanes of dihydroxyphenyl propane and 1,1-) Copolycarbonate.
The weight ratio of photo sensitive additive and fluoropolymer resin can be from 1:99 to 99:1, comprises from about 50:50 to about 85:15 or from about 10:90 to about 15:85.
In a particular embodiment, photo sensitive additive is formed by comprising following reaction: dihydroxy benaophenonel; Diol chain extender; Comprise the first linker part of multiple linking group, wherein the oh group of each linking group and dihydroxy benaophenonel and diol chain extender reacts; And end-capping reagent.In a particular embodiment, dihydroxy benaophenonel is 4,4'-dihydroxy benaophenonel.
In some embodiments, photo sensitive additive had 15 before uv light exposure, the weight-average molecular weight of 000 or larger.
Before uv light exposure, the mol ratio of dihydroxy benaophenonel and the first linker part can be from 1:2 to 1:200.
Crosslinkable polycarbonate resin can have use UV-VIS detector (UV-VIS detector, UV-VISdetector) and polycarbonate standards measured 17 by GPC and before uv light exposure, 000 to 80, between 000 dalton, or 17, weight-average molecular weight between 000 to 35,000 dalton.Crosslinkable polycarbonate resin sometimes had and uses UV-VIS detector and polycarbonate standards by the polydispersity index (PDI) between 2.0 and 3.0 measured by GPC before uv light exposure.Crosslinkable polycarbonate resin stops at 300 DEG C/1.2kg/360s the melt flow rate (MFR) that (dwell) place can have about 1 to about 40g/10min.The plate be made up of polycarbonate is at 36.0J/cm 2uL945VA performance can be obtained at 1.5mm (± 10%) thickness place after the ultraviolet radiation of UVA.
Blend can comprise fire retardant further.Fire retardant can be potassium perfluorobutane sulfonate (Rimar salt), sulfobenzide-3-potassium sulfonate (potassiumdiphenylsulfone-3-sulfonate) (KSS) or their combination.In a particular embodiment, fire retardant is Rimar salt, and this fire retardant exists with the amount of about 0.06wt% to about 0.08wt% based on the gross weight of composition.Concrete embodiment comprises fire retardant, comprises thermo-stabilizer and releasing agent further.
Blend can also comprise impact modifier, ultra-violet stabilizer, tinting material, fire retardant, thermo-stabilizer, softening agent, lubricant, releasing agent, filler, toughener (reinforcingagent), antioxidant, static inhibitor, pore forming material or stable radiation agent further.
In a particular embodiment, fluoropolymer resin is polycarbonate-polysiloxane copolymer.Polycarbonate-polysiloxane copolymer can have the content of siloxane from about 4wt% to about 8wt% based on the gross weight of blend.
Also disclose the various products formed by blend described here.In a particular embodiment, product is moulded product, film, plate (sheet), the layer of multilayer film or multiple-plate layer.Product can pass through injection molding, post forming (overmolding), coinjection moulding, extrudes, multilayer extrusion, rotoforming, blowing or thermoforming are formed.Product can be exposed to ultraviolet radiation thus cause the crosslinked of crosslinkable polycarbonate resin.
Also disclose the cross-linked layer formed by the polymeric blend being exposed to ultraviolet radiation, this blend comprises: photo sensitive additive, and this photo sensitive additive is containing the crosslinkable polycarbonate resin derived from the photosensitive group of dihydroxy benaophenonel; And fluoropolymer resin, this fluoropolymer resin is different from this photo sensitive additive.Cross-linked layer can containing the chain from photo sensitive additive and fluoropolymer resin.The crosslinked continuous insoluble layer that can be enough to produce containing photo sensitive additive and fluoropolymer resin.In a particular embodiment, cross-linked layer provides 0.5J/cm by being exposed to 2the ultraviolet of the filtration of UVA radiation and undetectable UVC radiation and formed.Cross-linked layer is at 36J/cm 2uL945VA performance can be obtained at 1.5mm (± 10%) thickness place after the ultraviolet radiation of UVA.
Below these and other non-restrictive characteristic will more specifically be described.
Accompanying drawing explanation
Here is the concise and to the point description of figure, and it presents the object for illustrating illustrative embodiments disclosed herein and is not the object for limiting it.
Fig. 1 shows and forms photo sensitive additive (oligomer/polymer) by the photosensitive part of difunctionality, the first linker part, diol chain extender and end-capping reagent.
Fig. 2 shows to be divided by the photosensitive part of difunctionality, the first linker part, diol chain extender, end-capping reagent and the second fixture body and forms side chain photo sensitive additive (oligomer/polymer).
Fig. 3 shows the cross-linking mechanism of photo sensitive additive.
Fig. 4 shows the figure of the FTIR spectrum of additive, polymkeric substance and gel.Some peak ratio shows to form cross-linked network.
Fig. 5 shows additive, different polymkeric substance and gel from 1200cm -1to 800cm -1the figure of FTIR spectrum when wave number.Some peak ratio shows to form cross-linked network.
Fig. 6 shows the additive of Fig. 5, polymkeric substance and gel from 1550cm -1to 1350cm -1the figure of FTIR spectrum when wave number.At 1452cm -1the peak at place appears in the spectrum of gel and polymkeric substance, shows the network be cross-linked.
Embodiment
More easily present disclosure can be understood wherein by reference to the embodiment of following hope and the detailed description of embodiment that comprises.In the following description with in claims, a large amount of term will be mentioned, and this term will be defined as there is following implication.
Unless otherwise defined, all technology used herein and scientific terminology have the identical meanings that those of ordinary skill in the art understand usually.In the case of a conflict, file of the present invention, comprises definition, will control.Preferred method and material are described below, although the method similar or suitable with material with method described here and material may be used for practice of the present invention or test.All publications, patent application, patent and referred in this other reference by reference its full content is incorporated into this.Material, method and example disclosed herein are only illustrative and are not intended to limit.
Unless the context clearly determines otherwise, otherwise singulative " ", " one " and " being somebody's turn to do " comprise the indicator of plural number.
As used in the specification and in the claims, term " comprise " can comprise embodiment " by ... composition " and " substantially by ... form ".As used in this, term " comprises " " comprising " " have " " having ", " can ", " containing " and variant thereof refer to open transitional phrases, term or word, it requires to exist composition/step of name and allows to there is other composition/step.But, such description also should be interpreted as composition or technique being described as " being made up of the composition/step enumerated " and " being substantially made up of the composition/step enumerated ", it allows to there is the composition/step only named, together with can consequent any impurity, and get rid of other composition/steps.
Numerical value in present specification and claims, particularly when they relate to polymkeric substance or polymer composition, the mean value of reflection composition, said composition can contain the independent polymkeric substance of different characteristics.In addition, unless the contrary indication, otherwise this numerical value should be understood to include when the identical figure place phase that convert significant figure to numerical value, and be less than the numerical value of traditional determination techniques experimental error of type described in the application's determined value with the difference of prescribed value.
All scopes disclosed herein comprise the end points and (such as, the scope of " from 2 grams to 10 grams " comprises end points, 2 grams and 10 grams, and all intermediate values) capable of being combined independently enumerated.End points and any value disclosed herein of scope are not limited to accurate scope or numerical value; They are not enough accurately thus the value comprised close to these scopes and/or value.
As used in this, approximate language can be applied thus modify any changeable quantificational expression, and not causing the change of relative basic function.Therefore, the value of being modified as " about " and " substantially " by a term or multiple term can be not limited to specified exact value in some cases.Under at least some example, approximate language can correspond to the precision of the instrument measuring this value.Modifier " about " also should be considered to disclose the absolute value limited range by two end points.Such as, express " about 2 to about 4 " and also disclose scope " from 2 to 4 ".Term " about " can relate to the plus or minus 10% of designation number.Such as, " about 10% " can comprise the scope of 9% to 11%, and " about 1 " can refer to 0.9-1.1.From the context, other implication of " about " can be obvious, and as rounded up, therefore, such as " about 1 " also can refer to from 0.5 to 1.4.
For enumerating in this numerical range, each between taking explicitly into account when same degree precision inserts number.Such as, for 6-9 scope, except 6 and 9, consider several 7 and 8, and for scope 6.0-7.0, take explicitly into account several 6.0,6.1,6.2,6.3,6.4,6.5,6.6,6.7,6.8,6.9 and 7.0.
Standardized denomination is used to describe compound.Such as, the appointed valence link of its valency is not interpreted as by any position that any appointment group replaces or hydrogen atom is filled.Short-term ("-") not between two letters or symbol is for representing substituent tie point.Such as, aldehyde group-CHO is connected by the carbon of carbonyl group.
Term " aliphatic " refers to it is not the arrayaof atoms of aromatic straight or branched.The main chain of aliphatic group is only made up of carbon.Aliphatic group can be substituted or unsubstituted.Exemplary aliphatic group includes but not limited to methyl, ethyl, sec.-propyl, hexyl and cyclohexyl.
Term " aromatic " refers to the group of the member ring systems of the delocalization conjugated pi system containing a large amount of π-electronics following H ü ckel rule.Member ring systems can comprise heteroatoms as nitrogen, sulphur, selenium, silicon and oxygen, or can only be made up of carbon and hydrogen.Aromatic group is not replace.Exemplary aromatic group includes but not limited to phenyl, pyridyl, furyl, thienyl, naphthyl and xenyl.
Term " ester " refers to the group of formula-CO-O-, and wherein carbon atom and Sauerstoffatom are all covalently bonded to carbon atom.
Term " carbonic ether " refers to the group of formula-O-CO-O-, and wherein Sauerstoffatom is all covalently bonded to carbon atom.Notice that carbonate group is not ester group, and ester group not carbonate group.
Term " hydroxyl " relates to the group of formula-OH, and wherein Sauerstoffatom is covalently bonded to carbon atom.
Term " alkyl " refers to the group be all made up of completely saturated carbon atom and hydrogen atom.Alkyl group can be straight chain, side chain or ring-type.
Term " aryl " refers to aromatic group, and it is only made up of carbon and hydrogen.Exemplary aromatic yl group comprises phenyl, naphthyl and xenyl.Note, " aryl " is aromatic subset.
Term " heteroaryl " refers to the aromatic group with the member ring systems be made up of carbon, hydrogen and at least one heteroatoms.Exemplary heteroaryl groups comprises pyridyl, furyl and thienyl.Note, " heteroaryl " is aromatic subset, and gets rid of " aryl ".
Term " halogen " refers to fluorine, chlorine, bromine and iodine.
Term " alkoxyl group " refers to the alkyl group be connected with Sauerstoffatom, that is ,-O-C nh 2n+1.
Term " aryloxy " refers to the aromatic yl group be connected with Sauerstoffatom, such as-O-C 6h 5.
Term " hydrocarbon " refers to the group be only made up of carbon and hydrogen.Alkyl and aryl are all considered to hydrocarbyl group.
Term " thiazolinyl " refers to the group be made up of carbon atom and hydrogen atom completely, and it contains is not at least one carbon-to-carbon double bond of aryl or heteroaryl moieties part.Alkenyl group can be straight chain, side chain or ring-type.Exemplary alkenyl group is vinyl (-CH=CH 2).
Term " alkene oxygen base " refers to the alkenyl group be connected with Sauerstoffatom, such as-O-CH=CH 2.
Term " aralkyl " refers to the aromatic yl group being connected to alkyl group, and wherein aromatic yl group is additional to parent molecule part by alkyl group, such as benzyl (-CH 2-C 6h 5).
Term " alkaryl " refers to the alkyl group being connected to aromatic yl group, and wherein alkyl group is additional to parent molecule part by aromatic yl group, such as tolyl (-C 6h 4-CH 3).
Term " amino " refers to formula R-NH 2group, wherein R is carbon atom.In order to the object of present disclosure, amino group is primary amino groups, namely containing two hydrogen atoms.
Term " carbamate " refers to the group of formula-NH-CO-O-, and wherein nitrogen-atoms and Sauerstoffatom are all covalently bonded to carbon atom.
Term " multipolymer " refers to relative with the homopolymer derived from unique a kind of structural unit or monomer, derived from the polymkeric substance of two or more structural units or monomeric species.
Term " C 3-C 6cycloalkyl " be cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Term " second-order transition temperature " or " Tg " refer to polymkeric substance as polycarbonate by have one or more useful performances maximum temperature.These performances comprise shock resistance, rigidity, intensity and shape-holding property.Particularly in plastic applications, therefore the Tg of polycarbonate can be the indicator of its useful upper temperature limit.Tg can use determine with dsc method, and degree Celsius to represent.Glass transition temp described here (Tg) is the tolerance of the thermotolerance of such as polycarbonate and polycarbonate Alloys.Tg by dsc such as by using TA instrument Q1000 instrument, such as, can be arranged 20 DEG C/min temperature rise rate (ramprate) and 40 DEG C of starting temperatures and 200 DEG C of end temps and measures.
Term " halogen " refers to that the substituting group be connected with prefix is replaced by one or more independent halogen group selected.Such as, " C 1-C 6alkylhalide group " refer to the C that wherein one or more hydrogen atoms are replaced by the halogen group independently selected 1-C 6alkyl substituent.C 1-C 6the unrestriced example of alkylhalide group comprises chloromethyl, 1-bromotrifluoromethane, methyl fluoride, difluoromethyl, trifluoromethyl and 1,1,1-trifluoroethyl.Will be appreciated that, if substituting group replaced by more than one halogen group, then these halogen groups can be identical or different (except as otherwise noted).
Term " turbidity " refers to the per-cent departing from the transmitted light of the incoming beam by forward scattering by sample.Per-cent (%) turbidity can be measured according to ASTMD1003-07.
Term " Melt Volume Rate " (MVR) or " melt flow rate (MFR) (MFR) " refers to the polymer flow speed in melt using the method for ASTMD1238-10 to determine.The MVR of molten polymer by determining that the amount of polymkeric substance is determined, this polymkeric substance use at a fixed temperature standard weights at the appointed time in flow through the kapillary of specified temp.MVR is expressed as cubic centimetre/10 minute, and MFR to be expressed as gram/10 minutes.MVR or the MFR value of polymkeric substance is higher at a certain temperature, and the flowing of this polymkeric substance under this specified temp is larger.
Term " percent transmittance " or " % transmittance " refer to the ratio of transmitted light and incident light, and can measure according to ASTMD1003-07.
" polycarbonate " used herein refers to the oligopolymer or polymkeric substance that comprise the monomer residue that one or more are connected by carbonic ether bonding.
" thermostability " relates to the resistance that polymkeric substance reduces molecular weight under heat condition as used in this.Thus, the polymkeric substance with weak thermostability under heat condition as extruding, be molded, thermoforming, can illustrate that significant molecular weight reduces during the condition such as hot pressing.Molecular weight is reduced and can also be formed by color and/or confirm as the reduction of weathering resistance, gloss, mechanical property and/or thermal property in other performance.Molecular weight is reduced in processing condition as caused noticeable change in melt viscosity change.
Term " is cross-linked " and its variant refers to form stable covalent linkage between two kinds of polymer/oligomer.This term is intended to comprise the covalent bonds being formed and cause network to be formed, or forms the covalent bonds causing chain extension.Term " crosslinkable " relates to the ability that polymer/oligomer forms so stable covalent linkage.
Present disclosure relates to " polymkeric substance ", " oligopolymer " and " compound ".The macromole that polymkeric substance is made up of the multiple repeating units linked together, repeating unit is derived from monomer.A kind of characteristic of polymkeric substance is that different polymer molecules will have different length, and polymkeric substance is described to the molecular weight of the mean value had based on chain (such as weight average or number-average molecular weight).This area is also distinguished " oligopolymer " and " polymkeric substance ", and oligopolymer only has some repeating units, and polymkeric substance has many repeating units.In order to the object of present disclosure, term " oligopolymer " refers to have and is less than 15, such molecule of the weight-average molecular weight of 000, and term " polymer " " refer to have and be greater than 15; the molecule of the weight-average molecular weight of 000, as used polycarbonate molecular weight standard by gpc measurement.In contrast, for compound, all molecules will have identical molecular weight.With polymer phase ratio, compound is small molecules.At these molecular weight of pre-test of any uv light exposure.
Present disclosure relates to photo sensitive additive (PAA), and is specifically related to the polymeric blend containing such additive.When interpolation photo sensitive additive is to one or more base resins and when being exposed to the suitable wavelength of light subsequently, the composition obtained will have anti-dripping melt and the flame retardant properties of improvement compared to one or more independent base resins or composition before light exposes.Such as, chemical resistant properties, the tendency (propensity) of dripping between main combustion period or the tendency forming hole when exposed to flame can be improved.The flame retardant properties characteristic improved can comprise flame out time (FOT) and Drain time (TTD).Blended or pure composition may be used for providing the thin-walled material adapting to UL945VA.Composition may be used for providing the thin-walled material adapting to 5VA and high-clarity.Composition can also show good chemical resistant properties, tear strength, shock strength, ductility, stability to hydrolysis and/or weathering resistance.Also consider the composition comprising the crosslinked polycarbonate formed by PAA.
Usually, the photo sensitive additive (PAA) of present disclosure comprises photosensitive part, and this photosensitive part is by the first linker part (firstlinkermoiety) and the second linker part is together covalently bound possibly.Photosensitive part contains photosensitive ketone groups, and this ketone groups will form stable covalent linkage when being exposed to one or more suitable wavelength of UV-light between PAA and polymer resin.PAA should blended in routine, formed and stablize under processing temperature (namely 350 DEG C more than stable).PAA also should not cause the degraded of the polymer resin blended with it.
The part that term " photosensitive part " refers to when being exposed to the UV-light of suitable wavelength and another kind is molecule crosslinked.Thus, such as, bisphenol A monomer in bisphenol A homopolycarbonate can not be considered to photosensitive part, even if when light-Fries rearrangement (photo-Friesrearrangement) can betide and be exposed to light, because atom does not participate in being cross-linked but only participates in the rearrangement of main polymer chain.
Photo sensitive additive formed by the reaction mixture containing at least the first photosensitive part and the first linker part.First photosensitive part comprises (i) ketone groups and (ii) two phenolic group groups.Fixture body is divided and is comprised multiple linking group, its can with the phenol radical reaction of the first photosensitive part.Reaction product is photo sensitive additive (PAA).First photosensitive part can be from 1:2 to 1:200 with the mol ratio of the first linker part.End-capping reagent is also contained in reaction mixture.As expected, also diol chain extender can be comprised.End-capping reagent and diol chain extender do not have photo-sensitive characteristic.
Term " ketone groups " relates to carbonyl group (-CO) (that is ,-the R-CO-R'-) that be bonded to two other carbon atoms.Two other carbon atoms can in aliphatic group or in aromatic yl group.Ester group and hydroxy-acid group are not considered ketone groups, because carbonyl group is bonded to a carbon atom and Sauerstoffatom.
Term " phenolic group group " relates to the phenyl group (-C of the oh group (-OH) with the carbon atom be covalently bond in phenyl group 6h 4-).
Photosensitive part can be dihydroxy phenyl ketone, and wherein, phenolic group group is directly bonded to ketone groups.The example of photosensitive part like this comprises those with one of formula (16)-(21) structure:
Wherein, R is H, alkyl or aryl.
The compound of formula (16) is dihydroxyphenyl phenyl ketone (dihydroxyphenyl-phenylmethanone).The compound of formula (17) is two (hydroxyphenyl) ketone.The compound of formula (16) or (17) can also be called as dihydroxy benaophenonel (dihydroxybenzophenone).The compound of formula (18) is 1-dihydroxyphenyl-2-phenylethane-1,2-diketone.The compound of formula (19) is two (hydroxyphenyl) ethane-1, the 2-diketone of 1,2-.The compound of formula (18) or (19) can also be called as dihydroxyl benzil (dihydroxybenzils).The compound of formula (20) is 1-(dihydroxyphenyl)-2--oxyl-2-Phenyl ethyl ketone.The compound of formula (21) is two (the hydroxyphenyl)-2--oxyl-ethyl ketone of 1,2-.
At some in other embodiment, R and the R' group being connected to ketone groups forms ring structure.In such embodiment, aromatic ring can comprise aryl rings or heteroaryl ring.The example of photosensitive part like this comprises those with one of formula (26)-(29) structure:
The compound of formula (26) and (27) is dihydroxyl dibenzo [1,3-e:1', 2'-f] [7] annulene-11-ketone (dihydroxydibenzo [1,3-e:1', 2'-f] [7] annulen-11-one).The compound of formula (28) and (29) is dihydroxyl thioxanthene-9-one (adihydroxythioxanthen-9-one).The position of different formulas reflection dihydroxyl group (on identical ring, or on different rings).
Photosensitive part and one or more first linker partial reaction.At least one first fixture body is divided and is comprised multiple functional group, this functional group can with the phenol radical reaction of photosensitive part.The example of such functional group comprises carboxylic acid (and acid anhydrides), acyl halide, alkyl ester and aryl ester.In general formula (A) below, these functional groups are shown:
Wherein, Y is hydroxyl, halogen, alkoxyl group or aryloxy.Functional group can be connected to aliphatic group or the aromatic group of " main chain " serving as linker part.In a particular embodiment, linker part can have two, three, four, even more functional group.
Have two functional groups and can with some examples of the first linker part of photosensitive partial reaction comprise have formula (30), one of (32) or (33) structure those:
Wherein, Y is hydroxyl, halogen, alkoxyl group or aryloxy; And wherein n is 1 to 20.It should be pointed out that formula (33) comprises m-phthalic acid and terephthalic acid.
There are three functional groups and those with one of formula (36)-(38) structure can be comprised with some examples of the first linker part of photosensitive partial reaction:
Wherein, Y is hydroxyl, halogen, alkoxyl group or aryloxy.
There are four functional groups and those with one of formula (39)-(41) structure can be comprised with some examples of the first linker part of photosensitive partial reaction:
Wherein, Y is hydroxyl, halogen, alkoxyl group or aryloxy.
In some embodiments, functional group can be provided by short oligopolymer, and this short oligopolymer comprises the oligopolymer containing glycidyl methacrylate monomer and vinylbenzene or methacrylate monomer, or epoxidized novolak resins.These oligopolymer can allow the functional group providing desired number.Such oligopolymer is summarized as the structure of formula (42):
Wherein, E is hydrogen or end-capping reagent, and p is the quantity of methacrylate monomer, and q is the quantity of methacrylate monomer, and r is the quantity of styrene monomer, and t is the quantity of epoxidation novolac (phenol formaldehyde (PF)) monomer.Usually, p+q+r+t≤20.When oligopolymer contains glycidyl methacrylate monomer and vinylbenzene or methacrylate monomer, usual t=0 and q >=1.Equally, for novolac resin, p=q=r=0.Epoxide group can with the phenol radical reaction of photosensitive part.
In special embodiment of wishing, photo sensitive additive can be formed by the reaction mixture containing photosensitive part, the first linker part and one or more diol chain extender (diolchainextender).Diol chain extender be only containing two oh groups molecule and be not photosensitive when exposed to light.When additive mixes with other polymer resin, chain propagation agent may be used for the blendability providing level of hope.Photo sensitive additive can comprise the diol chain extender of about 75wt% to about 99.5wt% or 95wt% to about 99mol% or about 80wt% to about 95wt% or about 80wt% to about 90wt%.
First exemplary diol chain extender is the bis-phenol of formula (B):
Wherein, R aand R brepresent halogen atom or monovalent hydrocarbon group separately and can be identical or different; P and q is the integer of 0 to 4 independently of one another; And the one in the group of A representative formula (B-1):
Wherein, R cand R drepresent hydrogen atom or monovalent straight chain or cyclic hydrocarbon group independently of one another and R eit is divalent hydrocarbyl mission.Such as, A replaces or unsubstituted C 3-C 18ring alkylidene (cycloalkylidene).
The specific examples of the type of the bisphenol cpd that can be represented by formula (B) comprises 1, two (4-hydroxyphenyl) methane, 1 of 1-, two (4-hydroxyphenyl) ethane, 2 of 1-, two (4-hydroxyphenyl) propane (hereinafter " dihydroxyphenyl propane " or " BPA "), 2 of 2-, two (4-hydroxyphenyl) butane, 2 of 2-, two (4-hydroxyphenyl) octane, 1 of 2-, two (4-hydroxyphenyl) propane, 1 of 1-, two (4-hydroxyphenyl) normal butane, 2 of 1-, two (4-hydroxyl-1-aminomethyl phenyl) propane of 2-and two (the 4-hydroxy-tert-butyl phenyl) propane of 1,1-; 4,4'-(1-phenylethane-1,1-bis-base) xenol or two (4-the hydroxyphenyl)-1-phenyl-ethane (bisphenol-ap) of 1,1-; Two (4-hydroxyphenyl)-3,3, the 5-trimethyl-cyclohexanes of 1,1-) (bis-phenol TMC).
Second exemplary diol chain extender is the bis-phenol of formula (C):
Wherein, each R kc independently 1-10hydrocarbyl group, n is 0 to 4.Halogen is bromine normally.The example of the compound that can be represented by formula (C) comprise Resorcinol, replacement resorcinol compound as oreinol diphenol, 5-phenyl Resorcinol or 5-cumyl Resorcinol; Catechol; Resorcinol; With the Resorcinol replaced as 2-methyl hydroquinone, 2-Tert. Butyl Hydroquinone, 2-phenyl Resorcinol, 2-cumyl Resorcinol or 2,3,5,6-duroquinol.
3rd exemplary diol chain extender is the biphenol polydiorganosiloxane of formula (D-1) or (D-2):
Wherein, each Ar is aryl independently; Each R is alkyl, alkoxyl group, thiazolinyl, alkene oxygen base, aryl, aryloxy, aralkyl or alkaryl independently; Each R 6divalence C independently 1-C 30organic group is as C 1-C 30alkyl, C 1-C 30aryl or C 1-C 30alkaryl; And D and E is the mean value of 2 to about 1000, particularly about 2 to about 500, or about 10 to about 200, or more specifically about 10 to about 75.
Show the specific examples of formula (D-1) or (D-2) below, such as formula (D-a) to (D-d):
Wherein, E is the mean value from 10 to 200.
4th exemplary diol chain extender is the aliphatic diol of formula (E):
Wherein, each X is hydrogen, halogen or alkyl independently; J is the integer from 1 to 20.The example of aliphatic diol comprises ethylene glycol, propylene glycol, 2,2-dimethyl-propylene glycol, 1,6-hexylene glycol and 1,12-dodecanediol.
5th exemplary diol chain extender is the dihydroxy compound of formula (F), and it can be useful for high temperature application:
Wherein, R 13and R 15halogen or C independently of one another 1-C 6alkyl group, R 14c 1-C 6alkyl, phenyl or utilization are up to five halogens or C 1-C 6the phenyl that alkyl group replaces, and c is 0 to 4.In a particular embodiment, R 14c 1-C 6alkyl or phenyl group.In another embodiment, R 14it is methyl or phenyl.In another embodiment, each c is 0.The compound of formula (F) comprises 3,3-bis-(4-hydroxyphenyl)-2-phenyl 1-isoindolinone (PPPBP).
Other dihydroxy compound (i.e. diol chain extender) can given as the polycarbonate height Tg of Copolycarbonate is the dihydroxy compound with adamantane units, as by reference it being all incorporated into this U.S. Patent number 7,112,644 and U.S. Patent number 3,516, described by 968.The repeating unit that the compound with adamantane units can have as shown in the formula (G) is used for high temperature application:
Wherein, R 1represent halogen atom, there is the alkyl group of 1 to 6 carbon atom, there is the alkoxy base of 1 to 6 carbon atom, there is the aromatic yl group of 6 to 12 carbon atoms, have 7 to 13 carbon atoms aryl substituted alkenyl group or there is the fluoroalkyl group of 1 to 6 carbon atom; R 2represent halogen atom, there is the alkyl group of 1 to 12 carbon atom, there is the alkoxy base of 1 to 12 carbon atom, there is the aromatic yl group of 6 to 12 carbon atoms, there is the alkenyl group that the aryl of 7 to 13 carbon atoms replaces or the fluoroalkyl group with 1 to 12 carbon atom; M represents the integer of 0 to 4; N represents the integer of 0 to 14.
Other dihydroxy compound can given as the polycarbonate height Tg of Copolycarbonate is the dihydroxy compound with fluorenes-unit, as U.S. Patent number 7, and 244, described by 804.By following formula (H), a kind of dihydroxy compound containing fluorenes-unit like this represents that being used for high temperature applies:
Wherein, R 1to R 4be hydrogen atom independently of one another, there is hydrocarbyl group or the halogen atom that can contain aromatic group of 1 to 9 carbon atom.
Operable another kind of diol chain extender is Isosorbide (isosorbide).Monomeric unit derived from Isosorbide can be the Isosorbide-bis-phenol unit of formula (I):
Wherein, R 1be isoscrbierite unit and R 2-R 9hydrogen, halogen, C independently of one another 1-C 6alkyl, methoxyl group, oxyethyl group or alkyl ester.
R 1isoscrbierite unit can be represented by formula (I-a):
Isoscrbierite unit can derived from the individual isomer of the mixture of the isomer of the mixture of Isosorbide, Isosorbide, Isosorbide and/or Isosorbide.Be not specifically limited the stereochemistry of the Isosorbide class carbonate unit for formula (I).These glycol can be prepared by the corresponding hexitol of dehydration (hexitol).From corresponding sugar (aldohexose) commercial production hexitol.Aliphatic diol comprises Isosorbide-5-Nitrae: 3,6-two dehydration-D sorbitol (Isosorbide-5-Nitrae: 3,6-dianhydro-Dglucitol); The two dehydration of Isosorbide-5-Nitrae: 3,6--D N.F,USP MANNITOL; The two dehydration of Isosorbide-5-Nitrae: 3,6--L iditol; With their any combination.Isosorbide is available commercially from different chemical supplier, comprises Cargill, Roquette and Shanxi.Isosorbide-bis-phenol can have the pKa between 8 and 11.
As previously explained, the first photosensitive part obtains photo sensitive additive with the first linker partial reaction.In some embodiments, the second fixture body is divided and is included in reaction mixture.Second linker part has at least three functional groups, wherein each can with the functional group reactions of the first linker part, and serve as branching agent.Usually, the functional group of the second linker part is oh group.
There are three functional groups and those with one of formula (43)-(46) structure can be comprised with some examples of the second linker part of the first linker partial reaction:
There are four functional groups and those with one of formula (47)-(48) structure can be comprised with some examples of the second linker part of the first linker partial reaction:
In some embodiments, the second linker part can be the oligopolymer be made up of epoxidation novolac monomer.These oligopolymer can allow the functional group providing desired number.The inductive structure of such oligopolymer through type (49):
Wherein, E is hydrogen or end-capping reagent; T is the integer from 1 to 20.
End-capping reagent is generally used for any polymer chain stopping photo sensitive additive.End-capping reagent (i.e. chain stopper) is monohydroxy compound, single acid compound or monoester compound.Exemplary end-capping reagent comprises phenol, p-cumylphenol (PCP), resorcinol monobenzoate, p-tert-butylphenol, octyl phenol, 4-hydroxybenzonitrile and p methoxy phenol.Term " end-capping reagent " is used herein to and represents when being exposed to the whether photosensitive compound of light.Such as, end-capping reagent is not containing ketone groups.Photo sensitive additive can comprise the capping group of the about 0.5mol% to about 5.0mol% derived from end-capping reagent.
Depend on the selection of the first linker part, the crosslinkable polycarbonate of present disclosure can be polyester-polycarbonate multipolymer.In polyester-polycarbonate, the mol ratio of ester units and carbonate unit can extensively change, such as 1:99 to 99:1, particularly 10:90 to 90:10, more specifically 25:75 to 75:25, depends on that the performance that final composition is wished expands alternatively.Polyester unit can derived from aliphatic dicarboxylic acid or aromatic dicarboxylic acid.Aliphatic dicarboxylic acid can have from 6 to about 36 carbon atoms, alternatively from 6 to 20 carbon atoms.Exemplary aliphatic dicarboxylic acid comprises adipic acid, sebacic acid, 3,3-dimethyl adipic acid, 3,3,6-trimethylammonium sebacic acid, 3,3,5,5-tetramethyl-sebacic acid, nonane diacid, dodecanedioic acid, dimer acids, cyclohexane dicarboxylic acid, dimethyl cyclohexane dicarboxylic acid, norbornane dicarboxylic acid, diamantane dicarboxylic acid, cyclohexene dicarboxylic acid, or C 14, C 18and C 20diacid.Exemplary aromatic dicarboxylic acid comprises m-phthalic acid or terephthalic acid, 1,2-bis-(to carboxyphenyl) ethane, 4,4'-dicarboxydiphenyl ether, 4,4'-two phenylformic acid; Isosorbide-5-Nitrae-, 1,5-, or NDA; And comprise the combination of at least one in above-mentioned acid.Concrete dicarboxylic acid mixture comprises the combination of m-phthalic acid acid and terephthalic acid, and wherein the weight ratio of m-phthalic acid and terephthalic acid is about 91:9 to about 2:98.
The polyester unit of polyester-polycarbonate can derived from isophthalic diformazan diacid and the combination of terephthaldehyde's diacid (or derivatives thereof) and the reaction of Resorcinol.In another embodiment, the polyester unit of polyester-polycarbonate can derived from m-phthalic acid and the combination of terephthalic acid and the reaction of dihydroxyphenyl propane.In embodiments, polycarbonate unit can derived from dihydroxyphenyl propane.In another kind of embodiment, polycarbonate unit can derived from Resorcinol and bisphenol-A, and the mol ratio of resorcinol carbonate unit and bisphenol a carbonate unit is 1:99 to 99:1.
The photo sensitive additive of present disclosure can be compound, oligopolymer or polymkeric substance.Oligopolymer has and is less than 15,000, comprises 10, the weight-average molecular weight (Mw) of 000 or less.The polymerization photo sensitive additive of present disclosure has 15, the Mw of 000 or higher.In a particular embodiment, Mw 17,000 and 80, between 000 dalton, or 17,000 and 35, between 000 dalton.Before any uv light exposure, measure these molecular weight.Mw can change as expected.The polymer/oligomer with higher Mw relatively retains their mechanical property usually better, and the polymer/oligomer simultaneously with lower Mw relatively has better flowing property usually.In some embodiments, the Mw of photo sensitive additive is about 5,000 or less.During melt-processed, such oligopolymer more likely rises to the surface of product.Long-chain fat race glycol (C 6or higher) also can be used for this object.This can be increased in the concentration of the additive of surface, and therefore also increases cross-linking density when being exposed to ultraviolet in surface.
The product deriving from the reaction in Fig. 1 is the example of such photo sensitive additive.Here, photo sensitive additive is formed by the first photosensitive part, the first linker part, diol chain extender and end-capping reagent.4,4' dihydroxy benaophenonel and phosgene, bisphenol-A and p-cumylphenol (end-capping reagent) react thus obtain photo sensitive additive.
The example of the photo sensitive additive formed is divided to see in Fig. 2 by the first photosensitive part, the first linker part, diol chain extender, end-capping reagent and the second fixture body.Here, 4,4'-dihydroxy benaophenonel and phosgene (the first linker part), bisphenol-A (diol chain extender), three (hydroxyphenyl) ethane (THPE, the second linker part) and p-cumylphenol (end-capping reagent) react thus obtain photo sensitive additive.Note, THPE (the second linker part) and phosgene (the first linker part) react, and do not react with 4,4'-dihydroxy benaophenonel (photosensitive part).The photo sensitive additive (PAA) obtained can be oligopolymer or the polymkeric substance with weight-average molecular weight and polydispersity index.
A kind of additive cross-linking mechanism is considered to owing to capturing hydrogen from alkyl group by ketone groups, and this alkyl group serves as hydrogen donor and couples the group of gained subsequently.This mechanism is figure 3 illustrates with reference to benzophenone (photosensitive part) and dihydroxyphenyl propane (BPA) monomer.When being exposed to ultraviolet, the Sauerstoffatom of benzophenone is from the methyl group abstract hydrogen atoms BPA monomer and become oh group.The carbon of methylene group and ketone groups forms covalent linkage subsequently.From another angle, the ketone groups of benzophenone can be considered to photosensitive group.It should be noted that the existence of hydrogen is crucial for this reaction.After capturing event at first, other mechanism can betide the base resin containing unsaturated link(age) or reactivity side group.
In a particular embodiment, photo sensitive additive disclosed herein (PAA) is the crosslinkable polycarbonate of the repeating unit comprised derived from dihydroxy benaophenonel monomer (i.e. formula (17)).Before crosslinked, these polycarbonate can be provided as heat-staple high melt flow polymer, and therefore may be used for manufacturing various thin-wall product (such as, 3mm or less).These products (such as, utilizing ultraviolet radiation) can be processed subsequently thus affect crosslinked, the thin-walled material meeting and wish performance requriements (such as, 5VA performance, chemical resistant properties, the transparency) is therefore provided.Crosslinked material, except flame retardant resistance and chemical resistant properties, compared to the composition before crosslinked, can keep or show excellent mechanical property (such as shock resistance, ductility).
The dihydroxy benaophenonel monomer of crosslinkable polycarbonate is provided for the photosensitive ketone groups of cross-linked polycarbonate.Utilize the crosslinkable polycarbonate of the treatment with uv radiation present disclosure being applicable to dosage, in dihydroxy benaophenonel carbonyl carbon and composition, in same polymer or another kind of polymkeric substance, the carbon atom of another functional group is (such as, the carbon atom of methylene radical, such as, in dihydroxyphenyl propane) between cause crosslinking reaction.
The crosslinkable polycarbonate of present disclosure comprises homo-polycarbonate, comprise the multipolymer of different piece in carbonic ether (being called " Copolycarbonate "), comprise carbonate unit and other type polymer unit as the multipolymer of polyester unit, polysiloxane unit and the combination comprising at least one homo-polycarbonate and Copolycarbonate.As a reference, term " dipolymer " refers to particularly derived from the multipolymer of two kinds of different monomers, and term " terpolymer " refers to particularly derived from the multipolymer of three kinds of different monomers.
If crosslinkable polycarbonate is multipolymer, then monomer can be incorporated in polycarbonate randomly.Random copolymers can have multiple block sequence and the alternate sequence of following statistical distribution.At random x:(1-x) in multipolymer, wherein x is the mol per-cent of the first monomer and 1-x is the mol per-cent of other monomer, such as, can use and pass through 13the peak area value that CNMR measures calculates the distribution of each monomer.Multipolymer can be alternating copolymer, it has I and O unit (-I-O-I-O-I-O-I-O-) alternately, or I and the O unit arranged in tumor-necrosis factor glycoproteins (such as there is following formula: the periodic copolymer (circulation multipolymer, periodiccopolymer) of (I-O-I-O-O-I-I-I-I-O-O-O) n).Crosslinkable Copolycarbonate can be statistical copolymer, and wherein monomer residue sequence follows statistical law.This multipolymer can also be segmented copolymer, and it comprises two or more the homopolymer subunits connected by covalent linkage (-I-I-I-I-I-O-O-O-O-O-).Homopolymer subunit combines can need middle non-repetitive subunit, is called connection block.The segmented copolymer with two or three different blocks is called as Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and triblock copolymer respectively.
In embodiments, the crosslinkable polycarbonate of present disclosure containing the 0.5mol% that has an appointment to the dihydroxy benaophenonel monomer (namely derived from the repeating unit of dihydroxy benaophenonel monomer) of about 50mol%.In embodiment more specifically, polymkeric substance containing the 1mol% to about 3mol% or about 1mol% that has an appointment to about 6mol%, about 10mol% to about 25mol%, or the dihydroxy benaophenonel monomer of about 0.5mol% to about 25mol%.
The crosslinkable polycarbonate of present disclosure can have the second-order transition temperature (Tg) being greater than 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C, 250 DEG C, 260 DEG C, 270 DEG C, 280 DEG C, 290 DEG C or 300 DEG C as used dsc to measure.In some embodiments, polycarbonate has the second-order transition temperature within the scope of about 120 DEG C to about 230 DEG C, about 140 DEG C to about 160 DEG C, about 145 DEG C to about 155 DEG C, about 148 DEG C to about 152 DEG C or about 149 DEG C to about 151 DEG C.
The crosslinkable polycarbonate of present disclosure can have 15,000 to about 80,000 dalton [± 1,000 dalton] or 15,000 to about 35,000 dalton [± 1,000 dalton] or about 20, the weight-average molecular weight (Mw) of 000 to about 30,000 dalton [± 1,000 dalton].In some embodiments, crosslinkable polycarbonate has about 16,000 dalton [± 1,000 dalton], about 17,000 dalton [± 1,000 dalton], about 18,000 dalton [± 1,000 dalton], about 19,000 dalton [± 1,000 dalton], about 20,000 dalton [± 1,000 dalton], about 21,000 dalton [± 1,000 dalton], about 22,000 dalton [± 1,000 dalton], about 23,000 dalton [± 1,000 dalton], about 24,000 dalton [± 1,000 dalton], about 25,000 dalton [± 1,000 dalton], about 26,000 dalton [± 1,000 dalton], about 27,000 dalton [± 1,000 dalton], about 28,000 dalton [± 1,000 dalton], about 29,000 dalton [± 1,000 dalton], about 30,000 dalton [± 1,000 dalton], about 31,000 dalton [± 1,000 dalton], about 32,000 dalton [± 1,000 dalton], about 33,000 dalton [± 1,000 dalton], about 34,000 dalton [± 1,000 dalton], or about 35, the weight-average molecular weight of 000 dalton [± 1,000 dalton].In other embodiment, crosslinkable polycarbonate has 17,000 to about 80,000 daltonian Mw.Gel permeation chromatography (GPC) can be used, use crosslinked styrene-divinylbenzene post and use the UV-VIS detector being set in 264nm place, or alternatively using refractive index detector to carry out molecular weight determination for polycarbonate reference calibrations.Sample can be prepared as the concentration of about 1mg/ml, and with the flow velocity elution samples of about 1.0ml/min.
The crosslinkable polycarbonate of present disclosure can have about 2.0 to about 5.0, about 2.0 to about 3.0 or the polydispersity index (PDI) of about 2.0 to about 2.5.PDI was measured before any uv light exposure.
It should be noted that the molecular weight (weight average and number are all) that can use two kinds of different types of detectors measure photo sensitive additive/crosslinkable polycarbonate.More specifically, use UV-light (UV) detector or use specific refractory power (RI) detector, use GPC and can molecular weight be measured for two kinds of detectors for polycarbonate standards calibration.
In embodiments, when using GPC method and polycarbonate molecular weight standard, the polydispersity index (PDI) using UV detector to measure is 1.4 or less with the ratio of the PDI using RI detector to measure.Ratio also can be 1.2 or less, or 1.1 or less.
The crosslinkable polycarbonate of present disclosure can have melt flow rate (MFR) (being often abbreviated as MFR), and its temperature in regulation and load place measure the rate of extrusion of composition passing hole.In some embodiments, use ASTMD1238 method, 1.2kg load, 300 DEG C of temperature, within 360 seconds, stop, polycarbonate can have the MFR of 1 to 40 gram/10min, 6 to 15 grams/10min, 6 to 8 grams/10min, 6 to 12 grams/10min, 2 to 30 grams/10min, 5 to 30 grams/10min, 8 to 12 grams/10min, 8 to 10 grams/10min or 20 to 30 gram/10min.
The crosslinkable polycarbonate of present disclosure can have the second-order transition temperature (Tg) being greater than 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C, 250 DEG C, 260 DEG C, 270 DEG C, 280 DEG C, 290 DEG C or 300 DEG C, as used measured by dsc.In some embodiments, polycarbonate has about 120 DEG C to about 230 DEG C, about 140 DEG C to about 160 DEG C, about 145 DEG C to about 155 DEG C, about 148 DEG C to about 152 DEG C, or about 149 DEG C of second-order transition temperatures to about 151 DEG C of scopes.
The crosslinkable polycarbonate of present disclosure can have 2wt% to 90wt%; 5wt% to 25wt%; 10wt% to 30wt%; 15wt% to 35wt%; 20wt% to 40wt%; 25wt% to 45wt%; 30wt% to 50wt%; 35wt% to 55wt%; 40wt% to 60wt%; 45wt% to 65wt%; 55wt% to 70%wt%; 60wt% to 75wt%; 50wt% to 80wt%; Or the biocontent of 50wt% to 90wt% (biocontent).Biocontent can be measured according to ASTMD6866.
The crosslinkable polycarbonate of present disclosure is at 1.3mm/min, 50mm span (span) place can have measured by ASTMD790 be more than or equal to 2200 megapascal (MPa)s (MPa), be more than or equal to 2310MPa, be more than or equal to 2320MPa, be more than or equal to 2330MPa, be more than or equal to 2340MPa, be more than or equal to 2350MPa, be more than or equal to 2360MPa, be more than or equal to 2370MPa, be more than or equal to 2380MPa, be more than or equal to 2390MPa, be more than or equal to 2400MPa, be more than or equal to 2420MPa, be more than or equal to 2440MPa, be more than or equal to 2460MPa, be more than or equal to 2480MPa, be more than or equal to the Young's modulus of 2500MPa.
In embodiments, the crosslinkable polycarbonate of present disclosure can have 2,200 to 2,500, and preferably 2,250 to 2,450, the more preferably modulus in flexure of 2,300 to 2,400MPa.In other embodiments, the crosslinkable polycarbonate of present disclosure can have 2,300 to 2,600, and preferably 2,400 to 2,600, the more preferably modulus in flexure of 2,450 to 2,550MPa.Also measure modulus in flexure by ASTMD790.
The crosslinkable polycarbonate of present disclosure can have measured by ASTMD638 type i with 50mm/min be more than or equal to 60 megapascal (MPa)s (MPa), be more than or equal to 61MPa, be more than or equal to 62MPa, be more than or equal to 63MPa, be more than or equal to 64MPa, be more than or equal to 65MPa, be more than or equal to 66MPa, be more than or equal to 67MPa, be more than or equal to 68MPa, be more than or equal to 69MPa, be more than or equal to 70MPa, be more than or equal to 71MPa, be more than or equal to 72MPa, be more than or equal to 73MPa, be more than or equal to 74MPa, be more than or equal to the tensile strength at breaking part of 75MPa.
The crosslinkable polycarbonate of present disclosure can have and at 3.2mm thickness is in-20 DEG C ,-15 DEG C ,-10 DEG C, 0 DEG C, 5 DEG C, 10 DEG C, 15 DEG C, 20 DEG C, 23 DEG C, 25 DEG C, 30 DEG C or 35 DEG C, is more than or equal to 60% in notched izod test according to ASTMD256-10, is more than or equal to 65%, is more than or equal to 70%, is more than or equal to 75%, is more than or equal to 80%, is more than or equal to 85%, is more than or equal to 90%, is more than or equal to 95%, or the ductility of 100%.
The crosslinkable polycarbonate of present disclosure can have measure at 23 DEG C according to ASTMD256 be more than or equal to 500J/m, be more than or equal to 550J/m, be more than or equal to 600J/m, be more than or equal to 650J/m, be more than or equal to 700J/m, be more than or equal to 750J/m, be more than or equal to 800J/m, be more than or equal to 850J/m, be more than or equal to 900J/m, be more than or equal to 950J/m or be more than or equal to the notched Chalpy impact intensity (NII) of 1000J/m.
The crosslinkable polycarbonate of present disclosure can have utilize the thick unannealed mm rod of 3.2mm in 1.82MPa place mensuration according to ASTMD648 be more than or equal to 110 DEG C, 111 DEG C, 112 DEG C, 113 DEG C, 114 DEG C, 115 DEG C, 116 DEG C, 117 DEG C, 118 DEG C, 119 DEG C, 120 DEG C, 121 DEG C, 122 DEG C, 123 DEG C, 124 DEG C, 125 DEG C, 126 DEG C, 127 DEG C, 128 DEG C, 129 DEG C, 130 DEG C, 131 DEG C, 132 DEG C, 133 DEG C, 134 DEG C, 135 DEG C, 136 DEG C, 137 DEG C, 138 DEG C, 139 DEG C, 140 DEG C, 141 DEG C, 142 DEG C, 143 DEG C, 144 DEG C, 145 DEG C, 146 DEG C, 147 DEG C, 148 DEG C, 149 DEG C, 150 DEG C, 151 DEG C, 152 DEG C, 153 DEG C, 154 DEG C, 155 DEG C, 156 DEG C, 157 DEG C, 158 DEG C, 159 DEG C, 160, 161 DEG C, 162 DEG C, 163 DEG C, 164 DEG C, 165 DEG C, 166 DEG C, 167 DEG C, 168 DEG C, 169 DEG C, or the heat-drawn wire of 170 DEG C.
The crosslinkable polycarbonate of present disclosure can have the percent haze value being less than or equal to 10.0%, being less than or equal to 8.0%, being less than or equal to 6.0%, being less than or equal to 5.0%, being less than or equal to 4.0%, being less than or equal to 3.0%, being less than or equal to 2.0%, being less than or equal to 1.5%, being less than or equal to 1.0%, being less than or equal to 0.5% measured at certain thickness place according to ASTMD1003-07.Polycarbonate turbidity can be measured at 2.0,2.2,2.4,2.54,2.6,2.8,3.0,3.2,3.4,3.6,3.8 or 4.0 mm of thickness places.Polycarbonate can be measured at 0.125 inch thickness place.
Polycarbonate can have measure at certain thickness place according to ASTMD1003-07 be more than or equal to 50%, be more than or equal to 60%, be more than or equal to 65%, be more than or equal to 70%, be more than or equal to 75%, be more than or equal to 80%, be more than or equal to 85%, be more than or equal to 90%, be more than or equal to 95%, be more than or equal to 96%, be more than or equal to 97%, be more than or equal to 98%, be more than or equal to 99%, be more than or equal to 99.1%, be more than or equal to 99.2%, be more than or equal to 99.3%, be more than or equal to 99.4%, be more than or equal to 99.5%, be more than or equal to 99.6%, be more than or equal to 99.7%, be more than or equal to 99.8%, or be more than or equal to the transmittance of 99.9%.Polycarbonate transparent degree can be measured at 2.0,2.2,2.4,2.6,2.8,3.0,3.2,3.4,3.6,3.8 or 4.0 mm of thickness places.
In some embodiments, the crosslinkable polycarbonate of present disclosure does not comprise soft segment or soft fat race section in polycarbonate chain.Such as, the polymkeric substance that soft section of the following aliphatics can got rid of from the crosslinkable polycarbonate of present disclosure comprises aliphatic polyester, aliphatic polyether, aliphatic poly thioether, aliphatic poly acetal, aliphatic polycarbonate, C-C connect and polysiloxane.Soft section of aliphatic polyester, aliphatic polyether, aliphatic poly thioether, aliphatic poly acetal, aliphatic polycarbonate can have the number-average molecular weight (Mn) being greater than 600.
In a particular embodiment, photosensitive crosslinkable polycarbonate resin formed by dihydroxy benaophenonel, diol chain extender, phosgene and one or more end-capping reagents.Most desirably, dihydroxy benaophenonel is 4,4'-dihydroxy benaophenonel.In a preferred embodiment, diol chain extender is dihydroxyphenyl propane, and end-capping reagent is p-cumylphenol.The photo sensitive additive (i.e. crosslinkable polycarbonate resin) obtained comprises the repeating unit derived from dihydroxy benaophenonel of about 0.5mol% to 25mol%.In embodiment more specifically, photo sensitive additive comprises the dihydroxy benaophenonel of the 1wt% to about 5mol% or about 5wt% to about 20wt% or about 10wt% to about 20wt% that has an appointment.
In a particular embodiment, crosslinkable polycarbonate is by the repeating unit derived from 4,4'-dihydroxy benaophenonel and bisphenol-A, and is not the multipolymer that photosensitive end-capping reagent forms.Multipolymer containing the 0.5mol% to 25mol% that has an appointment derived from the repeating unit of dihydroxy benaophenonel and about 75mol% to the 99.5mol% repeating unit derived from dihydroxyphenyl propane.
The interfacial polycondensation polymerization technique of bisphenol-A (BPA) class polycarbonate may be used for the photo sensitive additive (PAA) preparing present disclosure.Although the reaction conditions of interfacial polymerization can change, but exemplary technique is usually directed to dissolve in water or disperse one or more dihydric phenol reactant (such as dihydroxy benaophenonels, bisphenol-A), the mixture that interpolation obtains is in water-immiscible solvent medium, and under catalyzer (such as triethylamine, TEA) exists, make reactant contact carbonate precursor (such as phosgene).
Technique described here produces the polycarbonate with the polydispersity index (PDI) being less than 3 representatively.Higher PDI can represent the lower molecular weight mark increased in the product, and it can cause extruding the difficulty with injection molding technique by changing flow behavior or causing lower-molecular-weight component to volatilize outside material.
Four kinds of different techniques disclosed herein are for generation of some embodiments of the photo sensitive additive connected containing carbonic ether.Often kind of technique comprises following composition: dihydroxy benaophenonel, diol chain extender, end-capping reagent, carbonate precursor, alkali, tertiary amine catalyst, water and organic solvent immiscible with water, and branching agent alternatively.Dihydroxy benaophenonel is photosensitive part.It should be pointed out that in often kind of composition that being greater than one may be used for producing photo sensitive additive.Many in these compositions described above.
Carbonate precursor can be, such as, carbonyl halide, as phosphinylidyne dibromo or phosphinylidyne dichloro (also referred to as phosgene), or haloformate, as two haloformates (such as, ethylene glycol, two haloformates of neopentyl glycol, polyoxyethylene glycol etc.) of two haloformates (such as, two haloformates of dihydroxyphenyl propane, Resorcinol etc.) of dihydric phenol or ethylene glycol.The combination of at least one of the carbonate precursor comprising the above-mentioned type can also be used.In some embodiments, carbonate precursor is phosgene, triphosgene, diacyl halogen, two haloformates, dicyanate, diester, diepoxy resin (diepoxy), diaryl carbonate, dianhydride, diacid chloride (diacidchloride) or their any combination.The interface polymerization reaction forming carbonic ether connection can use phosgene as carbonate precursor, is called as phosgenation reaction.Many such carbonate precursors correspond to formula (30, (32), or the structure of (33).
Alkali is for adjusting the pH of reaction mixture.In a particular embodiment, alkali is alkali metal hydroxide, as sodium hydroxide (NaOH) or potassium hydroxide (KOH).
Tertiary amine catalyst is used for polymerization.Operable exemplary tertiary amine catalyst is aliphatic tertiary amine, as triethylamine (TEA), N-ethylpiperidine, 1,4-diazabicyclo [2.2.2] octane (DABCO), Tributylamine, cycloaliphatic amines, as N, N-diethyl-hexahydroaniline and aromatic nitrile base, as N, N-xylidene(s).
Sometimes, also phase-transfer catalyst is used.Formula (R among operable phase-transfer catalyst 30) 4q +the catalyzer of X, wherein each R 30be identical or different, and be C 1-C 10alkyl group; Q is nitrogen or phosphorus atom; X is halogen atom, C 1-C 8alkoxy base, or C 6-C 18aryloxy group.Exemplary phase-transfer catalyst comprises, such as, and [CH 3(CH 2) 3] 4nX, [CH 3(CH 2) 3] 4pX, [CH 3(CH 2) 5] 4nX, [CH 3(CH 2) 6] 4nX, [CH 3(CH 2) 4] 4nX, CH 3[CH 3(CH 2) 3] 3nX and CH 3[CH 3(CH 2) 2] 3nX, wherein X is Cl -, Br -, C 1-C 8alkoxy base or C 6-C 18aryloxy group, as methyltributylammonichloride chloride.
The most frequently used water-immiscible solvent comprises methylene dichloride, 1,2-ethylene dichloride, chlorobenzene, toluene etc.
In the first technique, sometimes referred to as in " (upfront) in advance " technique, combine dihydroxy benaophenonel, diol chain extender, end-capping reagent, catalyzer, water and with the immiscible solvent of water thus forming reactions mixture in a reservoir in advance.Reaction mixture is exposed to carbonate precursor subsequently, such as, by phosgenation, adds alkali altogether thus the pH of adjustment reaction simultaneously, thus obtains photo sensitive additive.
Be also referred to as in " solution interpolation " technique in the second technique, combine dihydroxy benaophenonel, diol chain extender, tertiary amine catalyst, water and with the immiscible solvent of water thus forming reactions mixture in a reservoir.Subsequently, in section, add total charging (charge) of carbonate precursor in a reservoir in this reaction mixture the total times of about 15 minutes to about 45 minutes, simultaneously jointly add alkali thus regulate pH.First time period within the scope of about 2 minutes to about 20 minutes, to be first added into carbonate precursor in reaction mixture together with alkali thus to regulate pH.After first time period terminates, add end-capping reagent in a controlled manner in reaction mixture, be also referred to as sequencing and add.Add end-capping reagent generation the second time period after a first period of time, instead of when reacting beginning (as in technique up front) as thing block (bolus).During the second time period, also with the addition of carbonate precursor and alkali together with end-capping reagent simultaneously.After the second time period terminated, within the 3rd time period, the continual continuation of remainder of carbonate precursor is until reach total charging.During the 3rd time period, also jointly add alkali thus regulate reaction pH.In first time period or during the 3rd time period, do not add end-capping reagent.Therefore photo sensitive additive is obtained.Reaction total time section is the summation of first time period, the second time period and the 3rd time period.In a particular embodiment, the second time period (wherein, adding containing the solution of end-capping reagent to reaction mixture) start from total time section 10% to the some place about between 40%.Alternatively, first time period be total time section 10%.
The third technique is also referred to as two-chloro-formic ester or chloro-formic ester (BCF) technique.Chloro-formic ester oligopolymer is reacted when there is not tertiary amine catalyst by carbonate precursor (being specially phosgene) and dihydroxy benaophenonel and diol chain extender and is prepared, and jointly adds alkali simultaneously thus regulates pH.Chloro-formic ester oligopolymer can contain the mixture of the oligopolymer of a chloro-formic ester, bischloroformates and bis-phenol end-blocking.After generation chloro-formic ester oligopolymer, phosgene concentrated or hydrolysis fully can be allowed alternatively, add end-capping reagent subsequently in chloro-formic ester mixture.Permission reaction is carried out, and adds tertiary amine catalyst thus complete reaction.
4th kind of technique uses tubular reactor.In a tubular reactor, end-capping reagent reacts with carbonate precursor (being specially phosgene) in advance thus forms chloro-formic ester.By the solvent be used as with the immiscible solvent of water in tubular reactor.In the reactor separated, by dihydroxy benaophenonel, diol chain extender, tertiary amine catalyst, water with combine thus forming reactions mixture with the immiscible solvent of water.In first time period, subsequently chloro-formic ester to be in a tubular reactor fed in reactor together with other carbonate precursor thus to complete reaction, simultaneously jointly add alkali thus regulate pH.
The photo sensitive additive (such as crosslinkable polycarbonate) obtained is only containing a small amount of lower-molecular-weight component.This can measure by two kinds of different modes: can measure diaryl carbonate (DAC) level and low per-cent.Diaryl carbonate is formed by two kinds of end-capping reagents and phosgene reaction, produces the small molecules not containing dihydroxy benaophenonel or diol chain extender (as dihydroxyphenyl propane).In embodiments, the photo sensitive additive obtained comprises the diaryl carbonate being less than 1000ppm.Low per-cent is the weight percent that molecular weight is less than the oligomer chain of 1000.In embodiments, low per-cent is 2.0wt% or less, comprises about 1.0wt% to 2.0wt%.DAC level and low per-cent can be measured by high performance liquid chromatography (HPLC) or gel permeation chromatography (GPC).Also noteworthy is that, the photo sensitive additive obtained does not contain any remaining pyridine, because do not use pyridine in the manufacture of photo sensitive additive.
Above-described photo sensitive additive and polymeric matrix (it is different from photo sensitive additive, i.e. the second fluoropolymer resin) blended thus form the blend of present disclosure.More specifically, the second fluoropolymer resin is not containing photosensitive group.In embodiments, the weight ratio of photo sensitive additive and polymeric matrix is 1:99 to 99:1, comprises about 50:50 to about 85:15 or about 10:90 to 15:85 or about 25:75 to about 50:50.In a particular embodiment, polymeric matrix has about 21, and 000 or larger, comprise about 21, the weight-average molecular weight of 000 to about 40,000.
Blend can stand cross linking conditions (such as, ultraviolet-radiation) thus carry out the crosslinked of photo sensitive additive in blend.Correspondingly, the blend composition of present disclosure comprises blend before crosslinking afterwards.
Blend can comprise one or more different described here crosslinkable polycarbonate, and/or one or more crosslinked polycarbonate as photo sensitive additive described here.Blend also comprises one or more other polymkeric substance.Blend can comprise other component, as one or more additives.In some embodiments, blend comprises crosslinkable and/or crosslinked polycarbonate (polymer A) and the second polymkeric substance (polymer B) and one or more additives alternatively.In another embodiment, blend comprises crosslinkable and/or crosslinked polycarbonate (polymer A); The combination of the second polycarbonate (polymer B), wherein the second polycarbonate is different from the first polycarbonate.
In a preferred embodiment, blend composition disclosed herein comprises fire retardant, flame-retardant additive and/or impact modifier.Fire retardant can be potassium perfluorobutane sulfonate (Rimar salt), sulfobenzide-3-potassium sulfonate (KSS) or their combination.
Second polymkeric substance (polymer B) can be any polymkeric substance being different from the first polymkeric substance (being suitable in blend composition).In some embodiments, second polymkeric substance can be polyester, polyestercarbonate, bisphenol A homopolycarbonate, Copolycarbonate, tetrabromobisphenol a polycarbonate multipolymer, polysiloxane-altogether-bisphenol-a polycarbonate, polyesteramide, polyimide, polyetherimide, polyamidoimide, polyethers, polyethersulfone, polyepoxide, polylactide, poly(lactic acid) (PLA), or their any combination.
In some embodiments, the second polymkeric substance can be vinyl polymer, rubber-modified graft copolymer, acrylate copolymer, polyacrylonitrile, polystyrene, polyolefine, polyester, polyesteramide, polysiloxane, urethane, polymeric amide, polyamidoimide, polysulfones, polyepoxide, polyethers, polyimide, polyetherimide, polyphenylene oxide, polyphenylene sulfide, polyetherketone, polyethers ether copper, acrylonitrile-butadiene-styrene (ABS) (ABS) resin, acrylicstyrene-vinyl cyanide (ASA) resin, polyethersulfone, Polyphenylene Sulfone, poly-(alkenyl aroma race) polymkeric substance (poly (alkenylaromatic) polymer), polyhutadiene, polyacetal, polycarbonate, polyphenylene oxide, vinyl-vinyl acetate copolymer, polyvinyl acetate, liquid crystalline polymers, ethylene-tetrafluoroethylene copolymer, aromatic polyester, fluorinated ethylene propylene, polyvinylidene difluoride (PVDF), polyvinylidene chloride, tetrafluoroethylene, polylactide, poly(lactic acid) (PLA), polycarbonate-organopolysiloxane segmented copolymer, or comprise (i) aromatic ester, (ii) ester carbonic ether, (iii) multipolymer of carbonate repetitive unit.Blend composition can comprise other polymkeric substance (the such as the 3rd, the 4th, the 5th, the 6th etc. polymkeric substance).
In some embodiments, the second polymkeric substance can be homo-polycarbonate, Copolycarbonate, polycarbonate-polysiloxane copolymer, polyester-polycarbonate or their any combination.In some embodiments, the second polycarbonate is poly-(isophthalic acid ester-terephthalate-resorcinol)-altogether-(bisphenol a carbonate) multipolymer of p-cumylphenol end-blocking.In some embodiments, the second polycarbonate is polycarbonate-polysiloxane copolymer.
Poly-(isophthalic acid ester-terephthalate-resorcinol)-altogether-(bisphenol-a carbonate) polymkeric substance of p-cumylphenol end-blocking or polycarbonate-polysiloxane copolymer can have the polysiloxane level of 0.4wt% to 25wt%.In one preferably embodiment, second polymkeric substance is poly-(19mol% isophthalic acid ester-terephthalate-resorcinol)-altogether-(75mol% bisphenol a carbonate)-altogether-(6mol% resorcinol carbonate) multipolymer (MW=29,000 dalton) of p-cumylphenol end-blocking.In another preferred embodiment, second polymkeric substance is poly-(10wt% isophthalic acid ester-terephthalate-resorcinol)-altogether-(87wt% bisphenol a carbonate)-altogether-(3mol% resorcinol carbonate) multipolymer (MW=29,000 dalton) of p-cumylphenol end-blocking.
In another kind preferably embodiment, the second polymkeric substance is polycarbonate-polysiloxane copolymer.Polycarbonate-polysiloxane copolymer can be comprise about 6wt% siloxanes (± 10%) to about 20wt% siloxanes (± 10%), and has the siloxane blocks Copolycarbonate of the siloxane chain length of 10 to 200.In another kind preferably embodiment, the second polymkeric substance is the PC-silicone copolymers with 20% siloxanes section by weight.In another kind preferably embodiment, second polymkeric substance is poly-(65mol%BPA the carbonic ether)-altogether-(35mol%3 of p-cumylphenol end-blocking, two (4-hydroxyphenyl)-2-phenyl 1-isoindolinone (PPPBP) carbonic ether of 3-) multipolymer (MW=25,000 dalton).
In another preferred embodiment, the second polymkeric substance is polyphosphonates polymkeric substance, polyphosphonates multipolymer or poly-(polyphosphonates)-altogether-(BPA carbonic ether) multipolymer.
In still other embodiment, fluoropolymer resin is in the blend selected from by the following group formed: polycarbonate-polysiloxane copolymer; Polycarbonate resin, this polycarbonate has aliphatic chain containing at least two carbon atoms in the polymer backbone as repeating unit; Copolyester polymer; Bisphenol A homopolycarbonate; Poly styrene polymer; Poly-(methyl methacrylate) polymkeric substance; Thermoplastic polyester; Polybutylene terephthalate polymkeric substance; MBS; Acrylonitrile-butadiene-styrene copolymer; Dimethyl bisphenol cyclohexane-altogether-bisphenol-A copolymer; Polyetherimide; Polyethersulfone; And two (4-hydroxyphenyl)-3,3, the 5-trimethyl-cyclohexanes of dihydroxyphenyl propane and 1,1-) Copolycarbonate (BPTMC).
In a particular embodiment, fluoropolymer resin is in the blend polycarbonate-polysiloxane (PC-Si) multipolymer.The polycarbonate unit of multipolymer is derived from the dihydroxy compound with any structure in above-described formula, but those in the chain extension agent of formula (B) and (C) (when Z is hydroxyl) especially.Some exemplary examples of suitable dihydroxy compound comprise following: 1,1 pair of (4-hydroxyphenyl) methane, 1, two (4-hydroxyphenyl) ethane, 2 of 1-, two (4-hydroxyphenyl) propane (hereinafter " dihydroxyphenyl propane " or " BPA "), 2 of 2-, two (4-hydroxyphenyl) butane, 2 of 2-, two (4-hydroxyphenyl) octane, 1 of 2-, two (4-hydroxyphenyl) propane, 1 of 1-, two (4-hydroxyphenyl) normal butane, 2 of 1-, two (4-hydroxyl-1-tolyl) propane of 2-and two (the 4-hydroxy-tert-butyl phenyl) propane of 1,1-; Resorcinol, the resorcinol compound of replacement, as oreinol diphenol, 5-phenyl Resorcinol or 5-cumyl Resorcinol; Catechol; Resorcinol; The Resorcinol replaced, as 2-methyl hydroquinone, 2-Tert. Butyl Hydroquinone, 2-phenyl Resorcinol, 2-cumyl Resorcinol or 2,3,5,6-duroquinol.Dihydroxyphenyl propane is usually the part of PC-Si multipolymer.
The polysiloxane of multipolymer is embedding can derived from the dihydroxy monomers of silicone-containing.A kind of exemplary siloxanyl monomers has the structure of formula (D-1):
Wherein, each Ar is aryl independently; Each R is alkyl, alkoxyl group, thiazolinyl, alkene oxygen base, aryl, aryloxy, aralkyl independently, or alkaryl; D is 2 to about 1000, particularly about 2 to about 500, and the more specifically mean value of about 10 to about 75.Under condition of phase transition, the compound of this formula can be obtained by dihydroxy aromatic compounds and the reaction of such as α, ω-bis--oxyethyl group-polydiorganosiloxane.
Another kind of exemplary siloxanyl monomers has the structure of formula (D-3):
Wherein, each R is alkyl, alkoxyl group, thiazolinyl, alkene oxygen base, aryl, aryloxy, aralkyl or alkaryl independently; D is 2 to about 1000, particularly about 2 to about 500, and the more specifically mean value of about 10 to about 75; Each M is cyano group, nitro, alkyl, alkoxyl group, thiazolinyl, alkene oxygen base, aryl, aryloxy, aralkyl or alkaryl independently; Each n is the integer from 0 to 4 independently; And each R 2aliphatic group independently.The compound obtaining this formula can be reacted by silicone hydride and the unsaturated monohydric phenol of aliphatics.The unsaturated monohydric phenol of suitable aliphatics comprises such as oxymethoxyallylbenzene, 2-alkylphenol, 4-allyl group-2-methylphenol, 4-allyl group-2-phenylphenol, 4-allyl group-2-tert.-butoxy phenol, 4-phenyl-2-phenylphenol, 2-methyl-4-propylphenol, 2-allyl group-4,6-xylenol, 2-allyl group-6-methoxyl group-4-methylphenol and 2-allyl group-4,6-xylenol.The mixture comprising above-mentioned middle at least one can also be used.
Fluoropolymer resin (polymer B) in the blend can be polycarbonate resin, and this polycarbonate resin has aliphatic chain containing at least two carbon atoms in the polymer backbone as repeating unit.This resin also can be considered to " soft section of polycarbonate " (SSP) resin.In general, SSP resin is the multipolymer of aromatic series difunctional compound and aliphatics difunctional compound.Aromatic series difunctional compound can have, and such as, in previously described formula (B)-(J), the structure of any one is as chain extension agent above.In a particular embodiment, aromatic series difunctional compound is the bis-phenol of formula (B).Aliphatics difunctional compound provides long aliphatic chain and can have the structure of formula (E) in main chain.Exemplary aliphatic diol useful in SSP resin comprises adipic acid (n=4), sebacic acid (n=8) and dodecanedioic acid (dodecanedioicacid) (n=10).
Such as, the phosgenation can passing through dihydroxyphenyl propane, sebacic acid and p-cumylphenol forms SSP resin.SSP resin contains carbonic ether connection and is connected with ester.
In this respect, think, photo sensitive additive crosslinking reaction speed and and its output be directly related to hydrogen in polymeric blend and ketone ratio.Thus, hydrogen higher in blend and ketone ratio, chain-amplified reaction/cross-linked speed should be higher.Because the rich hydrogen SSP resin with aliphatics block exists, hydrogen and ketone ratio are relative high.Therefore, cross-linking density should be very suitable for this blend with the flame retardant resistance obtained and chemical resistant properties.In addition, SSP resin has good mobility.Think, blend should also have good flowing, even and if also should keep its ductility after crosslinking.
Fluoropolymer resin (polymer B) in the blend can be copolyester polymer or polybutylene terephthalate (PBT) polymkeric substance.Conjugated polyester resin is commercially available, such as, under coming from Eastman chemical company TRITAN trade mark.PBT resin is commercially available, such as, under coming from SABICInnovativePlastics trade name VALOX.
Fluoropolymer resin (polymer B) in the blend can be bisphenol A homopolycarbonate.Such resin can obtain, such as, come from the LEXAN of SABICInnovativePlastics.
Fluoropolymer resin (polymer B) in the blend can be poly styrene polymer.Such polymkeric substance contains unique polystyrene monomers.Thus, such as ABS and MBS should not be considered to poly styrene polymer.
Fluoropolymer resin (polymer B) in the blend can be thermoplastic polyester.Exemplary polyester is PCTG, and it is the multipolymer of the reaction derived from terephthalic acid, ethylene glycol and cyclohexanedimethanol (CHDM).PCTG multipolymer can contain 40-90mol%CHDM, has the terephthalic acid and ethylene glycol of supplying remaining 10-60mol%.
Fluoropolymer resin (polymer B) in the blend can be dimethyl bisphenol cyclohexane-altogether-bisphenol-A copolymer, i.e. DMBPC-BPA multipolymer.This multipolymer illustrates below:
Wherein, the mol ratio of DMBPC and BPA is m:n.In addition, this symbol is intended to be reported in the relative molecular weight between DMBPC unit and BPA unit, and should not be interpreted as the structure representing multipolymer (namely these two unit are random distribution and are not blocks).DMBPC is 20mol% to 90mol% normally, comprises the multipolymer of 25mol% to 60mol%.BPA is 10mol% to 80mol% normally, comprises the multipolymer of 40mol% to 75mol%.These resins have high scuff resistance.
Other conventional additive (such as fire retardant, thermo-stabilizer, impact modifiers, UV stable additive, releasing agent, tinting material, organic and mineral filler, γ-stablizer etc.) can also be added in blend.
Dissimilar fire retardant can be used as additive.In one embodiment, flame retardant additives comprises, and such as, fire retardant salt, as fluoridized C 1-C 16an alkali metal salt of alkyl sulfonic ester, as potassium perfluorobutane sulfonate (Rimar salt), Perfluorooctane sulfonates potassium, perfluorohexanesulfonic acid Tetrylammonium, potassium diphenylsulfone sulfonate (KSS) etc., benzene sulfonic acid sodium salt, toluenesulfonic acid sodium salt (NATS) etc.; The salt formed is reacted: such as basic metal or alkaline-earth metal (such as lithium, sodium, potassium, magnesium, calcium and barium salt) and mineral acid complex salts, such as, oxo-anions, as the alkali and alkaline earth metal ions salt of carbonic acid, as Na with passing through 2cO 3, K 2cO 3, MgCO 3, CaCO 3, and BaCO 3or fluorine anion complex compound, as Li 3alF 6, BaSiF 6, KBF 4, K 3alF 6, KAlF 4, K 2siF 6, and/or Na 3alF 6deng.Rimar salt and KSS and NATS, separately or with other flame retardant combination, be useful especially in composition disclosed herein.In some embodiments, fire retardant is not containing bromine or chlorine.
Fire retardant is the such as aromatic sulfonic acid ester of monomer or polymerization or the Halogen metalloid salt of its mixture alternatively.Metal-salt is, such as, and the metal-salt of basic metal or alkaline earth salt or mixing.The metal of these groups comprises sodium, lithium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, francium and barium.The example of fire retardant comprises Phenylsulfonic acid caesium and tosic acid caesium.See such as, US3,933,734, EP2103654, and US2010/0069543A1, its full content is incorporated into this by content by reference disclosed in it.
Another useful class of fire retardant has general formula [(R) 2siO] ycyclosiloxane class, wherein R be there is the monovalence hydrocarbon of 1 to 18 carbon atom or fluorinated hydrocarbons and y be 3 to 12 numeral.The example of fluorinated hydrocarbons includes but not limited to 3-fluoropropyl, 3,3,3-trifluoro propyls, 5,5,5,4,4,3,3-hexafluoro amyl groups, fluorophenyl, difluorophenyl and fluoroform phenyl.The example of suitable cyclosiloxane includes but not limited to octamethylcyclotetrasiloxane, 1,2,3,4-tetramethyl--1,2,3,4-tetravinyl cyclotetrasiloxane, 1,2,3,4-tetramethyl--1,2,3,4-tetraphenyl cyclotetrasiloxane, octaethyl cyclotetrasiloxane, eight propyl group cyclotetrasiloxanes, eight butyl cyclotetrasiloxanes, decamethylcyclopentaandoxane, ten diformazan basic ring six siloxanes, tetradecamethylcycloheptasiloxane, ten pregnancy basic ring eight siloxanes, two decamethyl ring ten siloxanes, octaphenylcyclotetrasiloxane etc.Cyclosiloxane useful is especially octaphenylcyclotetrasiloxane.
Exemplary thermo-stabilizer additive comprises, and such as, organophosphite, as triphenyl phosphite, three-(2,6-3,5-dimethylphenyl) phosphorous acid esters, three-(list-of mixing and two-nonyl phenyl) phosphorous acid esters etc.; Phosphonic acid ester, as phosphonic acids diformazan phenyl ester etc.; Phosphoric acid ester, as trimethyl phosphite 99 etc.; Or comprise the combination of at least one in above-mentioned thermo-stabilizer.Based on the polymeric constituent of the polymeric blend/composition of 100 weight parts, thermo-stabilizer uses with the amount of 0.0001 to 1 weight part usually.
Permission material is removed by releasing agent (MRA) rapidly and effectively.The demoulding can reduce the brown stain of cycle index, defect and finished product.Between the material of these types, have sizable overlap, it can comprise, and such as, phthalic ester, as dioctyl-4,5-epoxies-hexahydro-phthalic acid ester; Three (octoxycarbonylethyl) isocyanuric acid ester; Stearin; Two-or multifunctional aromatic phosphoric ester, as two (phenylbenzene) phosphoric acid ester of resorcinol tetraphenyldiphosphate (RDP), Resorcinol and two (phenylbenzene) phosphoric acid ester of dihydroxyphenyl propane; Poly-alpha-olefin; Epoxy soybean oil; Silicone, comprises silicone oil; Ester, such as, fatty acid ester as allcyl stearate, such as, methyl stearate, stearyl stearate, pentaerythritol tetrastearate (PETS) etc.; The combination of methyl stearate and wetting ability and Hydrophobic nonionic tensio-active agent (comprise polyethylene glycol polymer, polypropylene glycol polymers, poly-(ethylene glycol-altogether-propylene glycol) multipolymer or comprise the combination of at least one in foregoing glycols polymkeric substance), such as, methyl stearate in a suitable solvent and polyethylene-polypropylene glycol copolymers; Wax, as beeswax, montanin wax, paraffin etc.Based on the polymeric constituent of the blend polymer/composition of 100 weight parts, consumption normally 0.001 to 1 weight part of this type of material, concrete 0.01 to 0.75 weight part, more specifically 0.1 to 0.5 weight part.
Polymeric blend can improve the chemical resistant properties of the finished product.Can be expected that, product can have the shape (such as film, plate etc.) of any hope and can be used for many different application, such as, in medical treatment, automobile, consumer electronics field.Find that the chemical resistant properties increased can for 409 glass and surface cleaner; Medical alcohol sheet; Slips liquid/slips rag; Slips cloth; Cidex liquid feeding; Sodium hypochlorite bleaching agent; Clorox rag; Envirocide liquid; ForPro liquid; Gentle dish soap and water; Hydrogen peroxide cleaning-sterilizing rag; Virahol rag; MadaCide-1 liquid; The Mar-V-Cide liquid of dilution; Sani-Cloth bleaches rag; Sani-ClothHB rag; Sani-Cloth adds rag; Sodium hypochlorite solution; Super Sani-Cloth rag; Viraguard liquid and rag; Virex256; WindexBlue; Fuel C; Toluene; Heptane; Ethanol; Virahol; Windex; Machine oil; WD40; Transmission fluid; Braking fluid; Glass washing composition; Diesel oil; Gasoline; Banana split sun-screening agent (BananaBoatSunscreen) (SPF30); Sebum; Ivory dish soap; SCJohnsonFantastik clearer; The yellow mustard of flag board; Coca-Cola; 70% Virahol; Extra Virgin; Vaseline Dermatology Formula Cream hand lotion; Heinz tomato-sauce; Kraft salad sauce; ChloroxFormula409 sanitising agent; There is the SCJohnsonWindex sanitising agent of ammonia; Acetone; Synthetic perspiration; Fruits & PassionCucina aster western & olive hand lotion; L'Oreal StudiolineMegagel hair jelly; MAYBELLINE lipstick; MaybellineExpertWear famille rose-beach plum lipstick; General riel Liquid soap; Hot black coffee; IKlear; Chlorox rag; Squalene; Palmitinic acid acid; Oleic acid; Zoomeric acid; Stearic acid; And sweet oil.
Preferably before crosslinked, composition disclosed herein/mixture can be formed, be shaped, molded, injection molding or be extruded into product, particularly thin-wall product, comprise the thin-wall product with the flame retardant properties of improvement and the highly transparent of good physical behavior.
Blend can be extruded into pellet, be molded subsequently or be extruded into product.Ultraviolet light irradiation product can be utilized subsequently thus produce crosslinked between chain, causing flame retardant resistance and the chemical resistant properties of improvement.PC-Si multipolymer is used to provide good shock strength and ductility at low temperatures, even if believe that blend will retain these performances after crosslinking.
Said composition/blend can in several ways as injection molding, post forming, coinjection moulding, extrude, multilayer extrusion, rotoforming, blowing and thermoforming mould make the product of useful shape thus form product.The product formed may stand cross linking conditions (such as, ultraviolet radiation) thus carry out polycarbonate to be cross-linked subsequently.
Composition may be used for providing material and product as but be not limited to, injection molding article, film, the plate extruded, fiber, pellet, flexibility-film, Tear resistant film and PVD laminating material.
The product that can be formed by composition/blend comprises the various assemblies of mobile phone and phone cover, computer case assembly, computer case and office machine housing and parts are as monitor case and parts, computer router, duplicating machine, desktop printer, larger office/industrial printer, handheld electronic device case is as computer or business machine housing, handheld device housing, light fixture or family or office equipment assembly, humidifier case, temperature controller case (temperature control equipment controls housing, thermostatcontrolhousings), air-conditioning discharge plate (airconditionerdrainpan), outdoor cabinet (outdoorcabinet), telecommunications shell and foundation structure, simple network intruding detection system (SNIDS) equipment, Network Interface Unit, smoke detector, assembly in plenum space and equipment, medical applications assembly or equipment are (as medical scanners, X-ray is equipped, and ultrasonic device), the assembly of automotive interior or external module, lens (automatically with non-automatic) are as film application component, greenhouse assembly, sun-room assembly, fire hat, safty shield (safetyshield), safety goggles, the glass of shock resistance, protecting sheet (fendors), protective shield (fenders), air pump, TV film (environment-friendlymembrane membrane as not halogen-containing composition), solar transmission material, glass laminates, glass-filled system fiber, hand-held electronic equipment shell or parts (such as walkie-talkie, scanner, media/MP3/MP4 player, receiving set, gps system, e-book, board), wearable electronic device (such as intelligent watch, training/tracking equipment, activity/sleep monitor system, wrist strap, or glasses), handheld tool shell or parts, smart phone shell or parts, turbine blade (such as, wind turbine) etc.
In some embodiments, the product that may comprise composition/blend comprises bumper, other automobile, building and Agricultural equipment external module, automobile mirrors housing (rear view mirror shell of automobile, automobilemirrorhousings), automobile grills (automobilegrille), automobile column (automobilepillar), wheel cover of automobile, automobile, building and Agricultural equipment dashboard and decoration, building and agriculture grid, automobile glove box, automotive door five metals (automobiledoorhardware) and other interior finishs, automobile building and agricultural equipment external modulation, trolley part in nacelle, pipe arrangement, valve and pump, air-conditioning heating and cooling parts, smelting furnace and heat pump components, machine element, electronic unit, projector components, electronic console parts, copier part, scanner components, electronic printer powder box, blower, flatiron, coffee machine, baking machine, washing machine, microwave oven, baking box, power tool, electric component, illuminace component, dental appliance and equipment, medicine equipment, cooker, medical appliance tray, cage for animal, fiber, laser welding medical facilities, hand-hold electronic equipments shell or parts (such as walkie-talkie, scanner, media/MP3/MP4 player, receiving set, gps system, e-book, board), wearable electronic device (such as intelligent watch, training/tracking equipment, activity/sleep monitor system, wrist strap, or glasses), handheld tool shell or parts, smart phone shell or parts, and optical fiber.
In some embodiments, the product that may comprise composition/blend comprises bumper, other automobile external assembly, automobile mirrors housing, automobile grills, automobile column, wheel cover of automobile, fascia and decoration, automobile glove box, automotive door five metals and other interior finish, outside automotive trim parts (as pillar), vehicle exterior, trolley part in nacelle, farm tractor or equipment unit, Architectural Equipment vehicle or equipment unit, building or agricultural equipment grid, boats and ships or individual ship parts (marineorpersonalwatercraftpart) waterborne, all-terrain vehicle (all-terrainvehicle) or all-terrain vehicle parts, pipe-line equipment (plumbingequipment), valve and pump, air-conditioning heating and cooling parts, smelting furnace and heat pump components, machine element, electronic unit, projector components, electronic console parts, copier part, scanner components, electronic printer powder box, blower, flatiron, coffee machine, baking machine, washing machine, microwave oven, baking box, power tool, electric component, electronic shell, illuminace component, dental appliance, medicine equipment, medical treatment or dentistry illuminace component, aircraft parts, train or rail parts, seat-assembly, sidewall, ceiling components, cooker, medical appliance tray, cage for animal, fiber, the medical facilities of laser welding, optical fiber, lens (automatically with non-automatic), mobile phone component, greenhouse assembly, sun-room assembly, fire hat, safty shield, safety glasses, protective shield, air pump parts, hand-hold electronic equipments shell or parts (such as walkie-talkie, scanner, media/MP3/MP4 player, receiving set, gps system, e-book, board), wearable electronic device (such as intelligent watch, training/tracking equipment, activity/sleep monitor system, wrist strap, or glasses), handheld tool shell or parts, smart phone shell or parts, and turbine blade.
In some embodiments, product needs maybe to comprise the product with UL945VA grade performance materials.The product of UL945VA grade is needed to comprise, but be not limited to, computer case, computer case and business machine housing and parts (as monitor case and parts), computer router, duplicating machine, desk tops printer, larger office/industrial printer, hand-hold electronic equipments shell (as computer or business machine housings), handheld device enclosure, comprise the lamp assembly of LED equipment or family or office equipment, humidifier case, temperature controller case, air-conditioning discharge plate, outdoor cabinet, telecommunications shell and foundation structure, simple network intruding detection system (SNIDS) equipment, Network Interface Unit, smoke detector, assembly in plenum space and equipment, medical applications assembly or equipment are (as medical scanners, X-ray is equipped, and ultrasonic device), electronic box and shell, and electric connector.
In some embodiments, product is a kind of product needing hydrothermal stability, as wind turbine blade, and the sterilizable medical facilities of steam, food service tray, utensil and equipment.
In some embodiments, product is a kind of product needing transparency, flame retardant resistance and/or shock resistance to combine.Such as, in some embodiments, product can be safty shield, safety goggles, gas/fuel pump casing, indicator gate or parts etc.
Product can be produced by manufacturing process.This technique can comprise step (a) provides the blend containing photo sensitive additive as above.Subsequently in an extruder such as 200-400 DEG C, melting can come from the blend of step (a) at 225-350 DEG C, 250-310 DEG C or 270-300 DEG C.The melt blended material of later step (b) can be extruded by (c), and (d) this blend can separated or chopping.The product manufactured can form blend by step (e) dry blends and (f) melting further and produce.Product can stand cross linking conditions described herein subsequently, to carry out the crosslinked of photo sensitive additive.In some embodiments, product is not subject to the impact of cross linking conditions after the fabrication immediately, but is cross-linked afterwards, such as, product is put into the DT.
Photo sensitive additive (PAA) can be blended thus form polymer composition/blend by melt blending or solution blending with one or more polymeric base resin.Subsequently can by various known technique (as solution-cast, section bar extrusion, film and/or plate extrude, plate foam is extruded, injection molding, blowing, thermoforming etc.) product will be formed containing the blend of PAA.Subsequently product is exposed in ultraviolet (UV) light (for the application given, this UV-light causes the crosslinked of desired amount) under suitable wavelength and suitable dosage.According to the application of end-use and the performance of hope, uv light exposure can be carried out in one or more surfaces of product.
Need the product of the performance strengthened should be exposed to the ultraviolet of substantially identical amount.Standard method known in the art is used to complete exposure.Such as, ultraviolet can come from any source of ultraviolet, e.g., but is not limited to, those lamp of being powered by microwave, HID lamp and mercury vapor lamps.In some other embodiments, product exposes by using natural sunlight.Open-assembly time will depend on application and the color of material.Its scope can be from several minutes to several days.Alternatively, can complete crosslinked by using ultraviolet transmitting illuminant (as mercury vapour, high-intensity discharge (HID) or various UV-lamp).Such as, the UV-lamp be purchased from manufacturers (as HereausNoblelightFusionUV) is for ultraviolet curing.The limiting examples of ultraviolet utilizing emitted light bulb comprises the mercury bulb (D bulb, H+ bulb, V bulb) of mercury lamp (H bulb) or metal halide doping.Also consider other combination of the metal halide producing ultraviolet light source.Exemplary bulb also can be produced by the lamp installed beyond ultraviolet-absorbing material and be considered to the ultraviolet source of filtration.The Jupiter of mercury of not adulterating is not used in radiation.H bulb has the strong output in 200nm to 320nm scope.D bulb has the strong output in 320nm to 400nm scope.V bulb has the strong output in 400nm to 420nm scope.
Use ultraviolet light source (wherein, damaging wavelengths (those cause polymer degradation or excessive xanthochromia) is removed or non-existent), this also can be favourable.Equipment supply business (as HeraeusNoblelightFusionUV) provide the lamp with different spectral distribution.Can also filtered light thus remove light that is harmful or undesired wavelength.Utilize optical filter to complete this, this optical filter is used for optionally transmission or refuses wavelength or wavelength region.These wave filters are available commercially from multiple company, as EdmundOptics or PraezisionsGlas & OptikGmbH.Design bandpass filter thus transmit a part of spectrum, and refusing other wavelength all.Design long-pass boundary filter thus transmit the wavelength being greater than filter cutoff wavelength.Short-pass boundary filter is less than the wavelength of filter cutoff wavelength for transmitting.Various types of material, as borosilicate glass, can be used as long wave pass.Such as, Schott and/or PraezisionsGlas & OptikGmbH has following long wave pass: WG225, WG280, WG295, WG305, WG320, and they have the cutoff wavelength of about 225,280,295,305 and 320nm respectively.These wave filters can be used for screening harmful short wavelength, transmit suitable wavelength simultaneously and are used for crosslinking reaction.
Ultraviolet wavelength can be divided into four kinds of different classifications.UVA refers to the wavelength of 320nm to 390nm.UVB refers to the wavelength of 280nm to 320nm.UVC refers to the wavelength of 250nm to 260nm.UVV refers to the wavelength of 395nm to 445nm.In some embodiments, filtering ultraviolet radiation thus the UVC that cannot detect radiation is provided, measuring as using EITPowerPuck.
In a particular embodiment, product is exposed to the ultraviolet light range of selection, and this scope has the wavelength of about 280 nanometers (nm) to about 380nm or about 330nm to about 380nm or about 280nm to about 360nm or about 330nm to about 360nm.Wavelength in " selection " optical range has the internal transmission rate being greater than 50%, has the wavelength outside the internal transmission rate scope being less than 50%.The change of transmissivity can occur within the scope of 20nm.The all wavelengths that the reference of the optical range selected should not be interpreted as in scope transmits with 100%, or all wavelengths outside scope is with 0% transmission.
The product exposed will have crosslinked outside surface and internal surface, and it is lightly crosslinked or noncrosslinking.Outside surface crosslinkable is to such degree thus make outside surface substantially be insoluble to common solvent for material resin.The per-cent of insolubles (undissolved component) will depend on the geometrical shape of parts and ratio that is surperficial and volume.
Following examples are provided thus illustrate the polymeric blend of present disclosure, product, technique and performance.These embodiments are only illustrative, and do not intend the disclosure to be defined in material, condition or processing parameter shown herein.
embodiment
The all solvents used and reagent are AG.
Use gel permeation chromatography (GPC), use crosslinked styrene-divinylbenzene post to carry out molecular weight determination and use the UV-VIS detector be set under 264nm to calibrate this molecular weight relative to polycarbonate references.Sample is prepared under the concentration of about 1mg/ml, and with the flow velocity wash-out of about 1.0ml/min.Alternatively, refractive index (RI) detector can be used.Per-cent change in molecular weight is calculated as change divided by the molecular weight before uv light exposure.
Adopt the dsc (DSC) of 20 DEG C/min temperature scan rate for determining the second-order transition temperature of polycarbonate.
Use standard underwriter laboratory UL94 testing method (2 days or process (adjustment) in 7 days) carries out combustibility test, unlike test 20 rod instead of common 5 rods.At room temperature pretreating specimen 48 hours or in air circulation oven at 70 ± 1 DEG C pretreating specimen 168 hours, subsequently before test, at room temperature in moisture eliminator, cool at least 4 hours.Once take out from moisture eliminator, at 30 minutes build-in test samples.
According to exercise question be " combustibility for plastic material is tested, UL94 (TestsforFlammabilityofPlasticMaterials, UL94) " Uderwriter laboratory bulletin 94 step carry out combustibility test.Whether burn based on the ability of rate of combustion, extinction time, anti-dripping melt and dropping, some grades can be applied.According to this step, based on the test result that 5 kinds of samples obtain, material can be divided into HB, V0, V1, V2,5V, 5VA and/or 5VB.Flammability class or " flame retardant resistance " standard are described as follows.
V0: sample is fixed with vertical direction and flame is put on the bottom of sample.Apply flame ten seconds, removing subsequently, until burning stops, now, more again applies flame another ten seconds and removes subsequently.Test two groups of five samples.At different conditions, two groups are processed.
In order to realize V0 grade, after test flame application, sample burns together with flame and must not exceed 10 seconds.The total flaming combustion time often organizing 5 samples must not exceed 50 seconds.Sample must not burn to sample gripping clamping apparatus together with flame or red-hot burning.Sample must not light the dropping burning particles of cotton.After removing test flame, do not have sample can have red-hot burning maintenance and be longer than 30 seconds.
5VA: test on rod and plate sample.The program of rod: excellent sample is fixed with vertical direction and flame put on an inferior horn place of sample with 20 ° of angles.Flame was applied 5 seconds, remove after 5 seconds.Flame is applied and removes repetition 5 times.Plate program: plate program is identical with excellent program, and difference is, plate sample level is laid and flame is put on the lower surface center of plate.
In order to realize 5VA grade, after five flame application, any flame of sample or red-hot burning must not exceed 60 seconds.Sample must not light the dropping burning particles of cotton.Plate sample must not present and burns in (hole).Note, embodiment is below with in table, and whether row (for given thickness, state 5VA is " passing through " or " failure ") only fingerboard test passes through, and should not be interpreted as showing that burning generation is not more than 60 seconds, and does not have dropping.The result reported 2 days and processed for 7 days.
By the computational analysis data of average extinction time, extinction time standard deviation and dropping sum.Statistical method is used for data-switching to become in concrete preparation will reach first time V0 in the standard UL94 test of 5 rods passing through or the probability of " p (FTP) ".Can determine according to following formula at the first probability submitting to the first time on (pFTP) to pass through:
PFTP=(P t1>mbt, n=0xP t2>mbt, n=0xP total <=mtbtx p dropping, n=0)
Wherein, P t1>mbt, n=0the probability not exceeding maximum combustion time value the first combustion time, P t2>mbt, n=0the probability not exceeding maximum combustion time value the second combustion time, P total <=mtbtthe probability that the summation of combustion time is less than or equal to value maximum total combustion time, and P dropping, n=0it is the probability not having sample to show drippage during flame test.Refer to the combustion time after the first and second flame application the first and second combustion times respectively.
Do not exceed the probability of maximum combustion time value the first combustion time, P t1>mbt, n=0can determine according to following formula: P t1>mbt, n=0=(1-P t1>mbt) 5wherein P t1>mbtbe the area under t1>mbt Lognormal distribution curve, and its Exponential " 5 " relate to the number of test rod.The probability not exceeding maximum combustion time value the second combustion time can be determined according to following formula: P t2>mbt, n=0=(1-P t2>mbt) wherein P t2>mbtfor the area under t2>mbt normal distribution curve.As above, combustion time data set mean value and standard deviation for calculating normal distribution curve.For UL-94V-0 grade, the maximum combustion time is 10 seconds.For V-1 or V-2 grade, the maximum combustion time is 30 seconds.During flame test, do not have sample to show the probability P of drippage dropping, n=0be attribute function, be estimated as: (1-P dropping) 5wherein P dropping=(the excellent number of the excellent number/test of drippage).
The summation of combustion time is less than or equal to the probability P of value maximum total combustion time total <=mtbtcan be determined by the normal distribution curve of 5 rod total combustion times of simulating.For data combustion time determined above, distribution is used to be simulated by the MonteCarlo of 1000 group of five rod and to produce distribution.The technology of MonteCarlo simulation is well known in the art.Use the mean value of 1000 groups of simulation and standard deviation can produce the normal distribution curve of 5 rod total combustion times.Therefore, for total <=maximum total combustion time, P total <=mtbtarea under the Lognormal distribution curve of the 5 rod total combustion times can simulated by one group of 1000MonteCarlo and determining.For UL94V0 grade, maximum total combustion time is 50 seconds.For V1 grade, maximum total combustion time is 250 seconds.
To reach the high confidence level of V0 grade for sample formulation in UL94 test, preferred p (FTP) value will be 1 or closely 1.
Under strained condition, evaluate the chemical resistant properties of cross-linked polycarbonate sample.The stretching rod of 3.2mm thickness is placed in strain fixture, with make fixture bending impel on stretching rod 0.5% or 1% stress level.By drippage solvent in the top of stretching rod, a part of rod is exposed to solvent.Allow rod to leave standstill 24 hours subsequently on fixture, make solvent evaporate during this period.Subsequently they taken out from strain fixture and under 50mm/min, be determined at the % elongation of breaking part according to ASTMD638I type method.
Sample is exposed to the ultraviolet of the filtration of various dose sometimes.Unfiltered light provides by using the FusionUV system of the bulb of D-bulb.The light filtered is provided by Loctite ζ 7411-S system, and it uses 400W metal halide arc lamps and behavior is similar to the bulb of D-bulb in the spectrum with 280-nm cutoff wavelength wave filter exports.For the UVA dosage (12,36 or 60J/cm of equivalence 2/ side), under UV-lamp on both sides exposed sample.The ultraviolet energy of each system (often by or dosage) is provided by Table A below, and uses EITPowerPuck to measure.Mensuration dosage is the energy of 320-390nm (UVA), 280-320nm (UVB), 250-260nm (UVC) and 395-445nm (UVV).Rapid Dose Calculation unit is J/cm 2.
Table A .Loctite (light of filtration)
Loctite dosage UVA UVB UVC UVV
Filter J/cm 2 J/cm 2 J/cm 2 J/cm 2
Within 320 seconds, expose 12.0 2.4 0 7.3
Within 960 seconds, expose 36.0 7.2 0 21.9
Within 1600 seconds, expose 60.2 12.1 0 36.6
Table B.Fusion (unfiltered light)
Fusion UV UVA UVB UVC UVV
Unfiltered J/cm 2 J/cm 2 J/cm 2 J/cm 2
Pass through for 2 times 12.0 3.7 0.45 5.8
Pass through for 6 times 35.9 11.0 1.34 17.5
Pass through for 10 times 59.9 18.3 2.24 29.2
Use CIELAB colour difference formula, 2 ° of viewing angles, and light source C uses the desk-top spectrophotometer of X-RiteColori7 within least 48 hours, to measure yellowness index (YI) on 3.2mm stretching rod before uv light exposure He after uv light exposure as light source in transmission mode.YI is measured according to ASTME313-73 (D1925).
Use ASTMD1238 method, 1.2kg load, 300 DEG C of temperature, within 360 seconds, stop the MFR calculating each sample.
Various embodiment can comprise the component of table shown in C.
Table C
Component Describe Trade(brand)name, source
Rimar Salt Potassium perfluor butane sulfonate Lanxess
Phosphite ester stabilizer Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester Irgaphos 168
embodiment 1
(A) preparation of crosslinkable polycarbonate
I () solution adds
sample A1
Use solution program to add and make sample A1 thus the crosslinkable polycarbonate resin obtaining 4, the 4'-dihydroxy benaophenonels (DHBP) containing 1.6mol%.
P-cumylphenol (193 grams, 0.91mol, 4.4mol%) solution is prepared in 500mL methylene dichloride.P-cumylphenol (PCP) solution is positioned in the interpolation tank (additionpot) be connected with reactor via volume pump (dosingpump).
Methylene dichloride (13L), DI water (10L), 4 is added in Preparation tank, 4'-dihydroxy benaophenonel (70 grams, 0.33mol, 1.6mol%), dihydroxyphenyl propane (4430 grams, 19.4mol), triethylamine (52 grams, 0.37mol) with gluconic acid sodium salt (10 grams, iron scavenging agent).Mixture is stirred 5 minutes, be transferred to the batch reactor of 70L subsequently, this reactor is equipped with the interpolation nozzle of overhead condenser, circulation loop, pH probe and different material.Wash this Preparation tank with methylene dichloride (8L), this washings is transferred in batch reactor.Open reactor agitator, and circular flow is set as 80L/min.Start phosgene steam flow reactor (80g/min flow velocity) by digital control system (DCS) and add original bulk (240 grams, 2.4mol).Controlled the NaOH aqueous solution of interpolation 33% by DCS, the pH of reaction is remained on the target of 10.0.
After the phosgene adding original bulk, controlled to be added in this reactor by DCS with the flow velocity of 500mL/min by PCP solution, phosgene continues to flow in reactor simultaneously.Phosgene adds and continues until reach total setting point (2400 grams, 24.3mol).After phosgene has added, obtain the sample of reactor and verified that this sample is not containing unreacted BPA and containing chloro-formic ester.Use ultraviolet rays detector by the Mw (Mw=21604, PDI=2.4) of GPC assaying reaction sample.Another batch of phosgene (200 grams, 2.0mol) is added in reactor.Use nitrogen purging reactor, shift this batch of material subsequently in separating centrifuge filling tank.
In separating centrifuge filling tank, add the methylene dichloride (8L) of dilution to this batch of material, use a series of this mixture of liquid centrifuge of fluid purifying subsequently.A separating centrifuge is separated salt face.Two separating centrifuges are by utilizing aqueous hydrochloric acid (pH1) extracting resin solution removal Triethylamine catalyst.Three to eight separating centrifuges are by utilizing DI water extracting resin solution removal survivor ion.Testing tree lipoprotein solution sample also demonstrates this sample chlorion with remaining triethylamine respectively lower than 5ppm.
Resin solution is transferred to precipitation feed chute.And then in toot, use the nitrogen of heating (210F) dry by steam precipitation and isolate white powder from resin.Powder produces 3855 grams.Mw＝21536PDI＝2.3。
sample A2
Use solution program to add and make sample A2 thus the crosslinkable polycarbonate resin obtaining 4, the 4'-dihydroxy benaophenonels (DHBP) containing 5.1mol%.
P-cumylphenol (196 grams, 0.92mol, 4.5mol%) solution is prepared in 500mL methylene dichloride.P-cumylphenol (PCP) solution is positioned in the interpolation tank be connected with reactor via volume pump.
Methylene dichloride (13L), DI water (10L), 4 is added in Preparation tank, 4'-dihydroxy benaophenonel (225 grams, 1.1mol, 5.1mol%), dihydroxyphenyl propane (4275 grams, 18.7 moles), triethylamine (52 grams, 0.37mol) with gluconic acid sodium salt (10 grams, iron scavenging agent).Mixture is stirred 5 minutes, be transferred to the batch reactor of 70L subsequently, this reactor is equipped with the interpolation nozzle of overhead condenser, circulation loop, pH probe and different material.Wash this Preparation tank with methylene dichloride (8L), this washings is transferred in batch reactor.Open reactor agitator, and circular flow is set as 80L/min.Start phosgene steam flow reactor (80g/min flow velocity) by DCS and add original bulk (240 grams, 2.4mol).Controlled the NaOH aqueous solution of interpolation 33% by DCS, the pH of reaction is remained on the target of 10.0.
After the phosgene adding original bulk, controlled to be added in this reactor by DCS with the flow velocity of 500ml/min by PCP solution, phosgene continues to flow in reactor simultaneously.Phosgene adds and continues until reach total setting point (2400 grams, 24.3mol).After phosgene has added, obtain the sample of reactor and verified that this sample is not containing unreacted BPA and containing chloro-formic ester.Use ultraviolet rays detector by the Mw (Mw=21761, PDI=2.3) of GPC assaying reaction sample.Another batch of phosgene (200 grams, 2.0mol) is added in reactor.Use nitrogen purging reactor, shift this batch of material subsequently in separating centrifuge filling tank.
In separating centrifuge filling tank, add the methylene dichloride (8L) of dilution to this batch of material, use a series of this mixture of liquid centrifuge of fluid purifying subsequently.A separating centrifuge is separated salt face.Two separating centrifuges are by utilizing aqueous hydrochloric acid (pH1) extracting resin solution removal Triethylamine catalyst.Three to eight separating centrifuges are by utilizing DI water extracting resin solution removal survivor ion.Testing tree lipoprotein solution sample also demonstrates this sample chlorion with remaining triethylamine respectively lower than 5ppm.
Resin solution is transferred to precipitation feed chute.And then in toot, use the nitrogen of heating (210F) dry by steam precipitation and isolate white powder from resin.Powder produces 3995 grams.Mw＝21454PDI＝2.2。
sample A3
Use solution program to make sample A3 thus obtain the crosslinkable polycarbonate resin of 4, the 4'-dihydroxy benaophenonels (DHBP) containing 10.1mol%.
P-cumylphenol (198 grams, 0.93mol, 4.5mol%) solution is prepared in 500mL methylene dichloride.P-cumylphenol (PCP) solution is positioned in the interpolation tank be connected with reactor via volume pump.
Methylene dichloride (13L), DI water (10L), 4 is added in Preparation tank, 4'-dihydroxy benaophenonel (450 grams, 2.1mol, 10.1mol%), dihydroxyphenyl propane (4050 grams, 17.7mol), triethylamine (52 grams, 0.37mol) with gluconic acid sodium salt (10 grams, iron scavenging agent).Mixture is stirred 5 minutes, be transferred to the batch reactor of 70L subsequently, this reactor is equipped with the interpolation nozzle of overhead condenser, circulation loop, pH probe and different material.Wash this Preparation tank with methylene dichloride (8L), this washings is transferred in batch reactor.Open reactor agitator, and circular flow is set as 80L/min.Start phosgene steam flow reactor (80g/min flow velocity) by DCS and add original bulk (240 grams, 2.4mol).Controlled the NaOH aqueous solution of interpolation 33% by DCS, the pH of reaction is remained on the target of 10.0.
After the phosgene adding original bulk, controlled to be added in this reactor by DCS with the flow velocity of 500mL/min by PCP solution, phosgene continues to flow in reactor simultaneously.Phosgene adds and continues until reach total setting point (2400 grams, 24.3mol).After phosgene has added, obtain the sample of reactor and verified that this sample is not containing unreacted BPA and containing chloro-formic ester.Use ultraviolet rays detector by the Mw (Mw=21732, PDI=2.3) of GPC assaying reaction sample.Another batch of phosgene (200 grams, 2.0mol) is added in reactor.Use nitrogen purging reactor, shift this batch of material subsequently in separating centrifuge filling tank.
In separating centrifuge filling tank, add the methylene dichloride (8L) of dilution to this batch of material, use a series of this mixture of liquid centrifuge of fluid purifying subsequently.A separating centrifuge is separated salt face.Two separating centrifuges are by utilizing aqueous hydrochloric acid (pH1) extracting resin solution removal Triethylamine catalyst.Three to eight separating centrifuges are by utilizing DI water extracting resin solution removal survivor ion.Testing tree lipoprotein solution sample also demonstrates this sample chlorion with remaining triethylamine respectively lower than 5ppm.
Resin solution is transferred to precipitation feed chute.And then in toot, use the nitrogen of heating (210F) dry by steam precipitation and isolate white powder from resin.Powder produces 4040 grams.Mw＝21523PDI＝2.2。
sample A4
Use solution program to add and make sample A4 thus the crosslinkable polycarbonate resin obtaining 4, the 4'-dihydroxy benaophenonels (DHBP) containing 20.1mol%.
P-cumylphenol (202 grams, 0.95 mole, 4.5mol%) solution is prepared in 500mL methylene dichloride.P-cumylphenol (PCP) solution is positioned in the interpolation tank be connected with reactor via volume pump.
Methylene dichloride (13L), DI water (10L), 4 is added in Preparation tank, 4'-dihydroxy benaophenonel (900 grams, 4.2mol, 20.1mol%), dihydroxyphenyl propane (3600 grams, 15.8mol), triethylamine (52 grams, 0.37mol) with gluconic acid sodium salt (10 grams, iron scavenging agent).Mixture is stirred 5 minutes, be transferred to the batch reactor of 70L subsequently, this reactor is equipped with the interpolation nozzle of overhead condenser, circulation loop, pH probe and different material.Wash this Preparation tank with methylene dichloride (8L), (this washings) is transferred in batch reactor.Open reactor agitator, and circular flow is set as 80L/min.Start phosgene steam flow reactor (80g/min flow velocity) by DCS and add original bulk (240 grams, 2.4mol).Controlled the NaOH aqueous solution of interpolation 33% by DCS, the pH of reaction is remained on the target of 10.0.
After the phosgene adding original bulk, controlled to be added in this reactor by DCS with the flow velocity of 500ml/min by PCP solution, phosgene continues to flow in reactor simultaneously.Phosgene adds and continues until reach total setting point (2400 grams, 24.3mol).After phosgene has added, obtain the sample of reactor and verified that this sample is not containing unreacted BPA and containing chloro-formic ester.Use ultraviolet rays detector by the Mw (Mw=21732, PDI=2.2) of GPC assaying reaction sample.Another batch of phosgene (200 grams, 2.0mol) is added in reactor.Use nitrogen purging reactor, shift this batch of material subsequently in separating centrifuge filling tank.
In separating centrifuge filling tank, add the methylene dichloride (8L) of dilution to this batch of material, use a series of this mixture of liquid centrifuge of fluid purifying subsequently.A separating centrifuge is separated salt face.Two separating centrifuges are by utilizing aqueous hydrochloric acid (pH1) extracting resin solution removal Triethylamine catalyst.Three to eight separating centrifuges are by utilizing DI water extracting resin solution removal survivor ion.Testing tree lipoprotein solution sample also demonstrates this sample chlorion with remaining triethylamine respectively lower than 5ppm.
Resin solution is transferred to precipitation feed chute.And then in toot, use the nitrogen of heating (210F) dry by steam precipitation and isolate white powder from resin.Powder produces 3314 grams.Mw＝21401PDI＝2.1。
Use similar technique to make other polycarbonate, but there is the DHBP of different amount and different molecular weight.Describe some in these other polycarbonate in Table 1.GPC and ultraviolet rays detector or RI detector is used to measure different character.Also show result in Table 1.The weight percentage of chain of molecular weight had lower than 1000 is shown in " low (lows) " list.
Table 1
Just as seen here, all solution adds the PDI ratio (UV/RI) that embodiment has 1.4 or lower.It should be noted that the ratio of sample A2 and sample A4 is lower than 1.0, may be due to measuring error.
blend example
embodiment 2
The sample of different size is by containing 4 of bisphenol-A and 1.6mol%, crosslinkable polycarbonate (XPC) multipolymer of 4'-dihydroxy benaophenonel (DHBP), make with p-cumylphenol (PCP) end-capping reagent, and have 21, the Mw of 536.XPC multipolymer with have Mw ≈ 31,000 low-the bisphenol-a polycarbonate homopolymer (LF-PC) that flows compares.Use the unfiltered ultraviolet coming from FusionUV system at 30J/cm 2uv light exposure before and after test the flame performance of these plates.Chemical resistant properties is measured by the elongation with the breaking part of the stretching rod of 3.2mm thickness.For flame performance, for each embodiment, the result of 48 hours is reported in left hurdle, and the result of 168 hours is reported in right hurdle simultaneously.Result illustrates in table 2.
Table 2
embodiment 3
Next, make XPC resin, this XPC resin comprises the DHBP of 5mol%, remaining as dihydroxyphenyl propane, and uses PCP end-capping reagent.This XPC resin has about 21, the Mw of 000.This XPC resin is blended with the low flowing bisphenol-a polycarbonate homopolymer (LF-PC) with Mw ≈ 31,000.
Subsequently, molded mouse is made up of blend, and is made up of LF-PC in contrast.Injection molding composition thus obtain molded mouse.Molded mouse is exposed to 36J/cm subsequently in Loctite system 2the ultraviolet of the filtration of UVA, end face is towards UV-lamp.In the gel thicknesses of three position finding mouses.The existence of gel coat shows crosslinkedly to occur.Also before uv light exposure, and 48 hours after uv light exposure determine the YI of mouse.Result is seen in table 3.
Table 3
Component E1 E2
5mol％DHBP@21K(phr) 50 0
LF-PC(phr) 50 100
Phosphite ester stabilizer (phr) 0.06 0.06
MFR(1.2kg/300℃,360s) 9.55 6.5
MFR(1.2kg/300℃,1080s) 9.92 6.49
The gel thicknesses (micron) of cover
Before 11.62 -
In 22.44 -
After 14.61 -
Average bulk part 16.23 -
The gel thicknesses (micron) of t-rod contrast 20.90 -
YI (unexposed) 0.16 -0.16
YI (being exposed to ultraviolet) 4.23 0.57
△YI 4.07 0.73
embodiment 4
Next, the XPC resin that test five kinds is different.Resin is the multipolymer of bisphenol-A and 4,4'-dihydroxy benaophenonel (DHBP), and uses PCP end-capping reagent.First resin contains the DHBP of 5mol% and has about 21, the target Mw of 000.Second resin contains the DHBP of 5mol% and has about 26, the target Mw of 000.3rd resin contains the DHBP of 10mol% and has about 21, the target Mw of 000.4th resin contains the DHBP of 10mol% and has about 26, the target Mw of 000.5th resin contains the DHBP of 20mol% and has about 21, the target Mw of 000.
Five kinds of XPC resins are blended from the low flowing bisphenol-a polycarbonate homopolymer (LC-PC) with Mw ≈ 31,000 of different amount, and test performance.Result is shown in table 4A and 4B.For flame performance, for each example, the result of 48 hours is reported in left hurdle, and the result of 168 hours is reported in right hurdle simultaneously.In Loctite system, carry out 36J/cm 2the uv light exposure of the ultraviolet of the filtration of UVA, top surface is to UV-lamp.Chemical resistant properties is measured at the elongation of breaking part by the stretching rod with 3.2mm thickness.
Table 4A
Table 4B
Blend usually has the larger increase of molecular weight after uv light exposure, and has lower MFR.Blend also has better chemical resistant properties than virgin resin.
embodiment 5
Next, by bisphenol-A formed and there is 4 of 20mol%, 4'-dihydroxy benaophenonel, residuum dihydroxyphenyl propane, with p-cumylphenol end-capping reagent and by about 21 of polycarbonate standards, the XPC-1 polycarbonate of the molecular weight of 000g/mol and other polymer blending, and be cast or be pressed into the film of 40-60 micron.
Those polymkeric substance are sebacic acid-altogether-bisphenol-A copolymers (SA-BPA); Copolyester polymer (coming from the TRITANTX1000 of Eastman); Poly styrene polymer (coming from the crystal polystyrene 585 of TotalPetrochemicals); Poly-(methyl methacrylate) polymkeric substance (PERSPEXCP-61); Dimethyl bisphenol cyclohexane-altogether-bisphenol-A copolymer (DMBPC-BPA, DMX1435); Thermoplastic polyester (PCTG) containing 80%CHDM; Polybutylene terephthalate polymkeric substance (VALOX195); There is the MBS (MBS) of 70% rubber content; There is the acrylonitrile-butadiene-styrene copolymer (ABS) of 16% rubber content.
Altogether make 12 kinds of compositions, be labeled as PCB-1 to PCB-12.PCB-1 is contrast, and is 100%XPC-1 (namely not having blend).As the second contrast, also use formed by dihydroxyphenyl propane and there are 4, the 4'-dihydroxy benaophenonels of 5mol%, residuum bisphenol-A, with p-cumylphenol end-capping reagent and by polycarbonate standards 26,000g/mol the also XPC-2 polycarbonate of molecular weight.Film is made subsequently by 12 kinds of compositions.PCB-1 to PCB-8 is supported in (25 × 75mm film) in sliding glass.PCB-9 to PCB-12 is pressed film forming (50mm diameter disk).
Use LoctiteUV system subsequently, the film formed is exposed to the ultraviolet radiation of filtration by 12 kinds of compositions.A surface is only had to be exposed in each film.By distinguishing exposed film 13 seconds, 19.5 seconds, 26 seconds, 54 seconds or 320 seconds, irradiate film 0.5,0.75,1.2 or 12J/cm simultaneously 2uVA energy.DSC is used to measure second-order transition temperature (Tg).
After exposure, film to be immersed in the methylene dichloride of 10mL and monitoring at any surplus materials of 48 hours.The existence of gel is taken as crosslinked index.Notice, any blend containing PCTG or PBT requires other solvent thus fully dissolves.These can be dissolved in the mixture of phenol and trichloroethane or by being repeatedly exposed in the mixture of methylene dichloride and cresols.
Result provides in table 5A and 5B.The amount of polymkeric substance is reported with weight percentage.If the quantity of gel equals the quantity of film, namely all films form continuous print gel coat, so utilize Y to represent crosslinked.If the quantity of gel is greater than the quantity of film, namely gel coat is segmented into several pieces, so utilizes G to mark them.If there is no visible gel, so utilize N marking composition.In the system utilizing immiscible blend, record two DSC values, wherein two Tg values remain different.
Except containing except the PCB-12 of ABS, all blends containing XPC-1 (20mol%DHBP) are being less than the gel forming indissoluble in 30 seconds.Six kinds in blend at 0.5J/cm 2place forms the gel of indissoluble.
Table 5A
Component PCB-1 PCB-2 PCB-3 PCB-4 PCB-5 PCB-6
XPC-1(20mol％) 100 50 80 80 80
XPC-2(5mol％) 100
SA-BPA 20
TRITAN 20
Polystyrene 50 20
Crosslinked@0UVA J/cm 2 N N N N N N
Crosslinked@0.5UVA J/cm 2 G N N G G G
Crosslinked@0.75UVA J/cm 2 G N G G G G
Crosslinked@1UVA J/cm 2 Y N G Y G G
Crosslinked@2UVA J/cm 2 Y G G Y Y Y
Crosslinked@12UVA J/cm 2 Y Y Y Y Y Y
DSC Tg(℃)@0UVA J/cm 2 146 146 105,146 144 105,146 109,145
DSC Tg(℃)@12UVA J/cm 2 150 147 107,147 146 103,148 106,147
The mol% of DHBP in composition 20 5 10 16 16 16
Table 5B
Component PCB-7 PCB-8 PCB-9 PCB-10 PCB-11 PCB-12
XPC-1(20mol％) 80 80 75 75 85 85
PMMA 20
DMBPC-BPA 20
PCTG 25
PBT Valox 195 25
MBS 15
ABS 15
Crosslinked@0UVA J/cm 2 N N N N N N
Crosslinked@0.5UVA J/cm 2 N G G N G N
Crosslinked@0.75UVA J/cm 2 G G G G G N
Crosslinked@1UVA J/cm 2 G G Y G G N
Crosslinked@2UVA J/cm 2 Y Y Y G G G
Crosslinked@12UVA J/cm 2 Y Y Y Y Y Y
DSC Tg(℃)@0UVA J/cm 2 146 146 122 118 147 109,144
DSC Tg(℃)@12UVA J/cm 2 148 147 120 115 146 107,143
The mol% of DHBP in composition 16 16 15 15 17 17
embodiment 6
Next, some other composition W01-W07 are made as blend.Blend comprises XPC-1 resin (20mol%DHBP), and other polymkeric substance.Loctite system is used to distinguish 40 seconds, 54 seconds, 80 seconds by exposed film in the ultraviolet filtered, or 320 seconds, film is exposed to 1.5,2,3 or 12J/cm 2uVA energy.The amount of polymkeric substance is reported with weight percentage.Result is reported in the mode identical with table 5A with 5B, and lists in table 6 below.
Table 6
Component W01 W02 W03 W04 W05 W06 W07
XPC-1(20mol％) 20 25 25 20 20 20 20
TRITAN 80
PCTG 75
PBT 75
Polystyrene 80
PMMA 80
SA-BPA 80
DMBPC-BPA 80
Crosslinked@0UVA J/cm 2 N N N N N N N
Crosslinked@1.5UVA J/cm 2 G G G G G G G
Crosslinked@2UVA J/cm 2 G G G G G Y G
Crosslinked@3UVA J/cm 2 G Y G G G Y Y
Crosslinked@12J/cm 2 Y Y G G G Y Y
DSC Tg(℃)@0UVA J/cm 2 118 95 104 105,144 136 133
DSC Tg(℃)@12UVA J/cm 2 117 99 105 103 135 140
Be separated N N Y Y Y N N
In W04 and W05, polystyrene and PMMA are dominant phases, and little and visible polycarbonate ball exists in the solution and floats after submergence.Transformation to continuous print gel coat does not occur, and it has this morphologic predictable result.Consider that continuous print gel coat is finally formed, other blend sample forms continuous print gel coat.This effect also sees W03, and wherein PBT stops continuous print gel to be formed on the surface exposed.Dsc analysis for W03 represents the peak not having different second-order transition temperatures.W03 is had to exist at the melt temperature peak at 221 DEG C of places.
embodiment 7
From the blend listed before, use XPC-1 and XPC-2 blended with LF-PC to expose some compositions under other dosage, and make other blend (B1-B3 of mark).In Loctite system, respectively by exposed film in the ultraviolet 26 seconds, 40 seconds, 54 seconds, 80 seconds or 320 seconds filtered, film is exposed to 1,1.5,2,3 or 12J/cm 2uVA energy.The amount of polymkeric substance is reported with weight percentage.Result is reported in the mode identical with table 5A with 5B, and lists in table 7 below.The row of Mw is the weight-average molecular weight by using the GPC of ultraviolet rays detector and polycarbonate standards to measure.
Table 7
Component B1 B2 W06 W07 B3 W02
XPC-1(20mol％) 20 20 20 25 25
LF-PC 80 75
XPC-2(5mol％) 100
SA-BPA 80
DMBPC-BPA 80
PCTG 75
The mol% of DHBP in composition 4 5 4 4 5 5
Crosslinked@1UVA J/cm 2 N N G G G N
Crosslinked@1.5UVA J/cm 2 G N Y G G G
Crosslinked@2UVA J/cm 2 G G Y G G G
Crosslinked@3UVA J/cm 2 G G Y Y G G
Crosslinked@12J/cm 2 Y Y Y Y Y Y
Mw@0UVA J/cm 2 24610 22401 26346 22316 - -
Mw@1UVA J/cm 2 28627 25692 36839 30841 - -
Mw@1.5UVA J/cm 2 29438 26115 40924 31483 - -
Mw@2UVA J/cm 2 34999 29374 49510 38279 - -
Mw@3UVA J/cm 2 35092 32085 63962 39890 - -
Mw@12UVA J/cm 2 46704 42098 56484 38466 - -
Notice, XPC-2 is at 1.5J/cm 2place does not produce visible gel, and wherein XPC-1 blend all represents some gel formation.Even if the DHBPmol% in XPC-1 composition is equal or the DHBPmol% that is less than in XPC-2 composition, this effect occurs.4mol%DHBP level is enough to satisfied crosslinked, as B1, W06, and shown in W07.At 1.5J/cm 2uVA place, blend containing SA-BPA (W06) forms continuous print gel coat, and simultaneously not crosslinked gel is present in XPC-2 film (B2).Usually, molecular weight increases along with uv light exposure, shows crosslinked generation.
At 12J/cm 2after UVA exposes, at PCB-1, W06, and the crosslinked gel section of W07 carries out FTIR, and after submergence, recover FTIR in methylene dichloride.On the powder type of SA-BPA and DMBPC-BPA, also carry out FTIR.The spectrum of PCB-1 gel fraction material is with comparing.Theory is, if W06/W07 has formed the crosslinked network containing XPC resin and other polymkeric substance (SA-BPA or DMBPC-BPA), so the FTIR of W06/W07 should have the signal at the peak of expression two compositions.
Fig. 4 shows the figure of the FTIR spectrum of PCB-1, SA-BPA and W07 gel.At 887cm -1and 929cm -1the peak ratio at place is significantly different in blend gel, shows that polymkeric substance is all incorporated in crosslinked gel coat.
Fig. 5 shows PCB-1, DMBPC-B{A and W07 gel, has from 1200cm -1to 800cm -1the figure of the FTIR spectrum of wave number.At 1100cm -1and 1114cm -1peak ratio be present in W07 gel and DMBPC-BPA spectrum, show that polymkeric substance is all incorporated in crosslinked gel coat.
Fig. 6 shows PCB-1, DMBPC-BPA and W07 gel, has from 1550cm -1to 1350cm -1the figure of the FTIR spectrum of wave number.At 1452cm -1the peak at place appears in W07 gel and DMBPC-BPA spectrum, is not present in control spectrum simultaneously.
FTIR data show that gel contains the crosslinked reaction product formed by XPC resin and other polymkeric substance simultaneously.
Next, XPC-3 polycarbonate is formed by the dihydroxyphenyl propane of the molecular weight with 3.45mol%4-dihydroxy benaophenonel (4-HBP) end-capping reagent and 22,000g/mol.The LF-PC resin alloy of XPC-1 and XPC-3 resin and different amount thus manufacture composition B1-B9.In Loctite system, by respectively exposed film in the ultraviolet filtered 40 seconds, 54 seconds, 80 seconds, or 320 seconds, film is exposed to 1.5,2,3, or 12J/cm 2uVA energy.The amount of polymkeric substance is reported with weight percentage.Result is listed in table 8 below.
Table 8
Component B2 B4 B3 B1 B5 B6 B7 B8 B9
XPC-1(20mol％DHBP) 100 30 25 20 10 5
LF-PC 70 75 80 90 95 42 70
XPC-3(3.45mol％4-HBP) 100 58 30
Benzophenone mol% in the composition 20 6 5 4 2 1 3.45 2 1.04
Crosslinked@0UVA J/cm 2 N N N N N N N N N
Crosslinked@1.5UVA J/cm 2 Y G G G N N N N N
Crosslinked@2UVA J/cm 2 Y Y G G G N G N N
Crosslinked@3UVA J/cm 2 Y Y Y G G G G N N
Crosslinked@12J/cm 2 Y Y Y Y Y G Y G N
At 12J/cm 2place, the blend of the 20mol%XPC-1 resin containing 10wt% illustrate yet still enough being cross-linked to form thus producing continuous print gel coat.Crosslinked gel formation in the B5 of dihydroxy benaophenonel with 2mol%, and fails to produce crosslinked gel as the respective sample B8 with the monohydroxy benzophenone of identical mol% of end-capping reagent.Total DHBP content and the characteristic of other resin are depended in the ultraviolet dosage change obtained needed for continuous print gel coat (Y).
embodiment 8
Polyetherimide (PEI, ULTEM1010) and the polyethersulfone (PES, ULTRASONE2010) of XPC-1 resin (20mol%DHBP, Mw about 21,000g/mol) and different amount are blended.These resins have high glass-transition temperature.Subsequently in Loctite system, by respectively exposed film in the ultraviolet filtered 54 seconds, 80 seconds, or 320 seconds, resin is exposed to 2,3, or 12J/cm 2uVA energy.Result is shown in table 9 below.Be cross-linked and be present in these examples.C1 and C2 unexpectedly forms continuous print gel coat.This is unexpected, because (a) film is almost opaque, expression is separated; B () PEI is from 250-395nm strong absorption UVA radiation.
Table 9
Component C1 C2 C3 C4 C5 C6
XPC-1(20mol％DHBP) 85 50 50 20
PEI 15 50 100
PES 50 80 100
Crosslinked@0UVA J/cm 2 N N N N N N
Crosslinked@2UVA J/cm 2 G G G G
Crosslinked@3UVA J/cm 2 Y G G G
Crosslinked@12J/cm 2 Y Y Y Y N N
The disclosure is described according to exemplary embodiment.Obviously, reading and other modifications and changes will occur after understanding detailed description above.Be intended that, fall within the scope of appended claims or Equivalent with regard to them, the disclosure is interpreted as comprising all such modifications and change.
In a word, polymeric blend, comprises: photo sensitive additive, and this photo sensitive additive is containing the crosslinkable polycarbonate resin derived from dihydroxy benaophenonel photosensitive group, and fluoropolymer resin, this fluoropolymer resin is different from this photo sensitive additive, and preferably, wherein the weight ratio of photo sensitive additive and fluoropolymer resin is about 10:90 to about 15:85, most preferably, wherein fluoropolymer resin is homo-polycarbonate, Copolycarbonate, polycarbonate-polysiloxane copolymer, polyester-polycarbonate, polyphosphonates polymkeric substance, polyphosphonates multipolymer, or poly-(isophthalic acid ester-terephthalate-resorcinol) of poly-(polyphosphonates)-altogether-(BPA carbonic ether) multipolymer or p-cumylphenol end-blocking-altogether-(bisphenol-a carbonate) multipolymer, poly-(isophthalic acid ester-terephthalate-resorcinol)-altogether-(bisphenol-a carbonate) polymkeric substance of such as p-cumylphenol end-blocking or there is the polycarbonate-polysiloxane copolymer of 0.4wt% to 25wt% polysiloxane level, wherein polycarbonate-polysiloxane copolymer comprises about 6wt% siloxanes (± 10%) to about 20wt% siloxanes (± 10%) to have the siloxane blocks Copolycarbonate of the siloxane chain length of 10 to 200 particularly, or alternatively wherein fluoropolymer resin is selected from by the following group formed: polycarbonate-polysiloxane copolymer, such as, there is based on the gross weight of blend the polycarbonate-polysiloxane copolymer of the content of siloxane of about 4wt% to about 8wt%, polycarbonate resin, this polycarbonate resin has aliphatic chain containing at least two carbon atoms in the polymer backbone as repeating unit, ethylene-acrylate-glycidyl acrylate terpolymer, copolyester polymer, bisphenol A homopolycarbonate, poly styrene polymer, poly-(methyl methacrylate) polymkeric substance, thermoplastic polyester, polybutylene terephthalate polymkeric substance, MBS, acrylonitrile-butadiene-styrene copolymer, dimethyl bisphenol cyclohexane-altogether-bisphenol-A copolymer, polyetherimide, polyethersulfone, two (4-hydroxyphenyl)-3,3, the 5-trimethyl-cyclohexanes of dihydroxyphenyl propane and 1,1-) Copolycarbonate.Alternatively, photo sensitive additive formed by the reaction comprising following (material): dihydroxy benaophenonel; Diol chain extender; Comprise the first linker part of multiple linking group, wherein the oh group of each linking group and dihydroxy benaophenonel and diol chain extender reacts; And end-capping reagent, preferably wherein end-capping reagent is selected from the group of following composition: phenol, p-tert-butylphenol, p-cumylphenol, octyl phenol, and 4-hydroxybenzonitrile; Photo sensitive additive had 15 before uv light exposure, the weight-average molecular weight of 000 or larger; And wherein the mol ratio of dihydroxy benaophenonel and the first linker part was 1:2 to 1:200 before uv light exposure alternatively.Alternatively, photo sensitive additive is crosslinkable polycarbonate resin, its had before uv light exposure by use the GPC of UV-VIS detector and polycarbonate standards to measure 17,000 and 80, weight-average molecular weight between 000 dalton, alternatively wherein crosslinkable polycarbonate resin there is the polydispersity index (PDI) between 2.0 and 3.0 by using the GPC of UV-VIS detector and polycarbonate standards to measure before uv light exposure and/or under 300 DEG C/1.2kg/360s stops about 1 to about 40g/10min melt flow rate (MFR).Or photo sensitive additive is crosslinkable polycarbonate resin, its under 300 DEG C/1.2kg/360s stops about 1 to about 40g/10min melt flow rate (MFR), and the plate formed by crosslinkable polycarbonate resin is at 36.0J/cm 2uL945VA performance can be realized at 1.5mm (± 10%) thickness place after the uviolizing of UVA.In above-mentioned blend, at least one in following condition can be applied: blend comprises fire retardant further, preferably wherein fire retardant is potassium perfluorobutane sulfonate (Rimar salt), sulfobenzide-3-potassium sulfonate (KSS), or their combination, more preferably wherein fire retardant exists with the amount of about 0.06wt% to about 0.08wt%; Blend comprises thermo-stabilizer and releasing agent further, alternatively together with impact modifier, ultra-violet stabilizer, tinting material, fire retardant, thermo-stabilizer, softening agent, lubricant, releasing agent, filler, toughener, antioxidant, static inhibitor, pore forming material, or stable radiation agent; The plate formed by blend realizes UL945VA grade at 1.5mm (± 10%) thickness.The product formed by blend can be moulded product, film, plate, the layer of multilayer film or multiple-plate layer, such as, by injection molding, post forming, coinjection moulding, extrude, multilayer extrusion, rotoforming, blowing, or thermoforming formed; And wherein product is exposed to ultraviolet radiation thus causes the crosslinked of crosslinkable polycarbonate resin.
In another embodiment, the cross-linked layer formed by the polymeric blend being exposed to ultraviolet radiation, comprising: photo sensitive additive, and this photo sensitive additive is containing the crosslinkable polycarbonate resin derived from dihydroxy benaophenonel photosensitive group; And fluoropolymer resin, this fluoropolymer resin is different from this photo sensitive additive, and preferably, wherein this cross-linked layer contains the chain coming from photo sensitive additive and fluoropolymer resin, more preferably, wherein crosslinked enough generations contain the insoluble layer of continuous print of photo sensitive additive and fluoropolymer resin; More preferably, wherein this cross-linked layer by being exposed to 0.5J/cm 2uVA radiation and the UVC radiation that cannot detect and being formed, and/or cross-linked layer is at 36J/cm 2uL945VA performance can be realized at 1.5mm (± 10%) thickness place after the uviolizing of UVA.

Claims (34)

1. a polymeric blend, comprises:
Photo sensitive additive, described photo sensitive additive is containing the crosslinkable polycarbonate resin derived from the photosensitive group of dihydroxy benaophenonel; With
Fluoropolymer resin, described fluoropolymer resin is different from described photo sensitive additive.
2. blend according to claim 1, wherein said fluoropolymer resin is polyester, polyestercarbonate, bisphenol A homopolycarbonate, Copolycarbonate, tetrabromobisphenol a polycarbonate multipolymer, polysiloxane-altogether-bisphenol-a polycarbonate, polyesteramide, polyimide, polyetherimide, polyamidoimide, polyethers, polyethersulfone, polyepoxide, polylactide, poly(lactic acid) (PLA) or their any combination.
3., according to described blend one or more in claim 1 or 2, wherein said fluoropolymer resin is vinyl polymer, the graft copolymer of modified rubber, acrylate copolymer, polyacrylonitrile, polystyrene, polyolefine, polyester, polyesteramide, polysiloxane, urethane, polymeric amide, polyamidoimide, polysulfones, polyepoxide, polyethers, polyimide, polyetherimide, polyphenylene oxide, polyphenylene sulfide, polyetherketone, polyethers ether copper, acrylonitrile-butadiene-styrene (ABS) (ABS) resin, acrylicstyrene-vinyl cyanide (ASA) resin, polyethersulfone, Polyphenylene Sulfone, poly-(alkenyl aroma race) polymkeric substance, polyhutadiene, polyacetal, polycarbonate, polyphenylene oxide, vinyl-vinyl acetate copolymer, polyvinyl acetate, liquid crystalline polymers, ethylene-tetrafluoroethylene copolymer, aromatic polyester, fluorinated ethylene propylene, polyvinylidene difluoride (PVDF), polyvinylidene chloride, tetrafluoroethylene, polylactide, poly(lactic acid) (PLA), polycarbonate-organopolysiloxane segmented copolymer, or comprise: (i) aromatic ester, (ii) ester carbonic ether, (iii) multipolymer of carbonate repetitive unit.
4., any one of claims 1 to 3 or multinomial described blend, wherein said fluoropolymer resin is poly-(isophthalic acid ester-terephthalate-resorcinol)-altogether-(bisphenol a carbonate) multipolymer of homo-polycarbonate, Copolycarbonate, polycarbonate-polysiloxane copolymer, polyester-polycarbonate or p-cumylphenol end-blocking.
5., any one of Claims 1-4 or multinomial described blend, wherein said fluoropolymer resin is poly-(isophthalic acid ester-terephthalate-resorcinol)-altogether-(bisphenol-a carbonate) polymkeric substance of p-cumylphenol end-blocking or has the polycarbonate-polysiloxane copolymer of 0.4wt% to 25wt% polysiloxane level.
6. blend according to claim 5, wherein said polycarbonate-polysiloxane copolymer is siloxane blocks Copolycarbonate, described siloxane blocks Copolycarbonate comprises about 6wt% siloxanes (± 10%) to about 20wt% siloxanes (± 10%), and has the siloxane chain length of 10 to 200.
7., any one of claim 1 to 6 or multinomial described blend, wherein said fluoropolymer resin is polyphosphonates polymkeric substance, polyphosphonates multipolymer or poly-(polyphosphonates)-altogether-(BPA carbonic ether) multipolymer.
8., any one of claim 1 to 7 or multinomial described blend, wherein said fluoropolymer resin is selected from by the following group formed: polycarbonate-polysiloxane copolymer; There is the aliphatic chain containing at least two carbon atoms polycarbonate resin as repeating unit in the polymer backbone; Ethylene-acrylate-glycidyl acrylate terpolymer; Copolyester polymer; Bisphenol A homopolycarbonate; Poly styrene polymer; Poly-(methyl methacrylate) polymkeric substance; Thermoplastic polyester; Polybutylene terephthalate polymkeric substance; MBS; Acrylonitrile-butadiene-styrene copolymer; Dimethyl bisphenol cyclohexane-altogether-bisphenol-A copolymer; Polyetherimide; Polyethersulfone; And two (4-hydroxyphenyl)-3,3, the 5-trimethyl-cyclohexanes of dihydroxyphenyl propane and 1,1-) Copolycarbonate.
9., any one of claim 1 to 8 or multinomial described blend, the weight ratio of wherein said photo sensitive additive and described fluoropolymer resin is about 10:90 extremely about 15:85.
10., any one of claim 1 to 9 or multinomial described blend, wherein said photo sensitive additive is formed by comprising following reaction:
Dihydroxy benaophenonel;
Diol chain extender;
Comprise the first linker part of multiple linking group, wherein the oh group of each linking group and described dihydroxy benaophenonel and described diol chain extender reacts; With
End-capping reagent.
11. blends according to claim 10, wherein said end-capping reagent is selected from by the following group formed: phenol, p-tert-butylphenol, p-cumylphenol, octyl phenol and 4-hydroxybenzonitrile.
12. blends according to claim 10 or 11, wherein said photo sensitive additive had 15 before uv light exposure, the weight-average molecular weight of 000 or larger.
13. according to claim 10 to any one of 12 or multinomial described blend, and wherein before uv light exposure, the mol ratio of described dihydroxy benaophenonel and described first linker part is from 1:2 to 1:200.
14. according to claim 10 to any one of 13 or multinomial described blend, wherein said photo sensitive additive is following crosslinkable polycarbonate resin, described crosslinkable polycarbonate resin had before uv light exposure use UV-VIS detector and polycarbonate standards by gpc measurement 17, weight-average molecular weight between 000 to 80,000 dalton.
15. according to claim 10 to any one of 14 or multinomial described blend, and wherein said crosslinkable polycarbonate resin had the polydispersity index (PDI) between 2.0 to 3.0 using UV-VIS detector and polycarbonate standards by gpc measurement before uv light exposure.
16. according to claim 10 to any one of 15 or multinomial described blend, and wherein said crosslinkable polycarbonate resin has the melt flow rate (MFR) of about 1 to about 40g/10min in 300 DEG C/1.2kg/360s stops.
17. additives according to claim 1, wherein said photo sensitive additive is the crosslinkable polycarbonate resin in 300 DEG C/1.2kg/360s stops with the melt flow rate (MFR) of about 1 to about 40g/10min, and the plate formed by described crosslinkable polycarbonate resin is at 36.0J/cm 2uL945VA performance can be obtained at 1.5mm (± 10%) thickness place after the ultraviolet radiation of UVA.
18. blends according to claim 1, comprise fire retardant further.
19. blends according to claim 18, wherein said fire retardant is potassium perfluorobutane sulfonate (Rimar salt), sulfobenzide-3-potassium sulfonate (KSS) or their combination.
20. blends according to claim 18, wherein said fire retardant exists with the amount of about 0.06wt% to about 0.08wt%.
21. blends according to claim 18, comprise thermo-stabilizer and releasing agent further.
22. any one of claim 1 to 21 or multinomial described blend, comprises impact modifier, ultra-violet stabilizer, tinting material, fire retardant, thermo-stabilizer, softening agent, lubricant, releasing agent, filler, toughener, antioxidant, static inhibitor, pore forming material or stable radiation agent further.
23. any one of claim 1 to 23 or multinomial described blend, and wherein said fluoropolymer resin is the polycarbonate-polysiloxane copolymer based on the gross weight of described blend with the content of siloxane of about 4wt% to about 8wt%.
24. any one of claim 1 to 23 or multinomial described blend, and the plate wherein formed by described blend obtains UL945VA grade at the thickness of 1.5mm (± 10%).
25. 1 kinds any one of claim 1 to 24 or the product that formed of multinomial described blend.
26. products according to claim 25, wherein said product be following at least one: bumper, automobile external assembly, automobile mirrors housing, automobile grills, automobile column, wheel cover of automobile, fascia or decoration, automobile glove box, automotive door five metals or other interior finish, vehicle exterior, trolley part in nacelle, farm tractor or equipment unit, apparatus for building vehicle or equipment unit, building or agricultural device grid, boats and ships or individual ship parts waterborne, all-terrain vehicle or all-terrain vehicle parts, pipe-line equipment, valve or pump, air-conditioning heating or cooling-part, smelting furnace or heat pump components, machine element, computer router, desktop printer, larger office/industrial printer, electronic unit, projector components, electronic console parts, copier part, scanner components, electronic printer powder box, blower, flatiron, coffee machine, baking machine, washing machine or part of washing machine, microwave oven, baking box, power tool, electric component, electrical enclosure, illuminace component, dental appliance, medicine equipment, medical treatment or dentistry illuminace component, aircraft parts, train or rail parts, seat-assembly, sidewall, ceiling components, cooker, medical appliance tray, cage for animal, fiber, the medical facilities of laser welding, optical fiber, lens (automatically with non-automatic), mobile phone component, greenhouse assembly, sun-room assembly, fire hat, safty shield, safety glasses, protective shield, air pump parts, humidifier case, temperature controller case, air-conditioning discharge plate, outdoor cabinet, telecommunications shell or foundation structure, simple network detection system (SNIDS) equipment, Network Interface Unit, smoke-detectors, assembly in plenum space or device, medical scanners, X-ray apparatus, building or agricultural device, palmtronic shell or parts, walkie-talkie shell or parts, scanner housing or parts, media/MP3/MP4 player casing or parts, wireless shell or parts, gps system shell or parts, e-book shell or parts, panel computer shell or parts, wearable electronic device, intelligent watch, wearable training/tracking equipment, wearable activity/sleep monitor system, wearable electronics watchband, electronic glass, handheld tool shell or parts, smart phone shell or parts, and turbine blade.
27. according to claim 25 or product according to claim 26, and wherein said product is moulded product, film, plate, the layer of multilayer film or multiple-plate layer.
28. any one of claim 25 to 27 or multinomial described product, wherein said product by injection molding, post forming, coinjection moulding, extrude, multilayer extrusion, rotoforming, blowing or thermoforming formed.
29. any one of claim 25 to 28 or multinomial described product, and wherein said product is exposed to ultraviolet radiation thus causes the crosslinked of described crosslinkable polycarbonate resin.
30. 1 kinds of crosslinked layers formed by the polymeric blend being exposed to ultraviolet radiation, described blend comprises:
Photo sensitive additive, described photo sensitive additive is containing the crosslinkable polycarbonate resin derived from the photosensitive group of dihydroxy benaophenonel; And
Fluoropolymer resin, described fluoropolymer resin is different from described photo sensitive additive.
31. layers according to claim 30, wherein said crosslinked layer contains the chain from described photo sensitive additive and described fluoropolymer resin.
32. according to claim 30 or layer according to claim 31, the wherein said crosslinked continuous insoluble layer being enough to produce containing described photo sensitive additive and described fluoropolymer resin.
33. any one of claim 30 to 32 or multinomial described layer, and wherein said crosslinked layer is by being exposed to 0.5J/cm 2uVA radiation and undetectable UVC radiation formation.
34. any one of claim 30 to 33 or multinomial described layer, and wherein said crosslinked layer is at 36J/cm 2uL945VA performance can be obtained at 1.5mm (± 10%) thickness place after the ultraviolet radiation of UVA.
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